Non-yellowing part-tertiary-alkyl phenyl substituted triazine and pyrimidine ultraviolet light absorbers

ABSTRACT

This invention relates generally to para-tertiary alkyl phenyl substituted pyrimidines and triazines and the use thereof to protect against degradation by environmental forces, inclusive of ultraviolet light, actinic radiation, oxidation, moisture, atmospheric pollutants and combinations thereof. The new class of para-tertiary alkyl phenyl substituted pyrimidines and triazines includes two tertiary alkylated phenyl groups, and a resorcinol or substituted resocinol group attached to the triazine or pyrimidine ring. These materials may, under the appropriate circumstances, be bonded to formulations comprising coatings, polymers, resins, organic compounds and the like via reaction of the bondable functionality with the materials of the formulation. A method for stabilizing a material by incorporating such para-tertiary alkyl phenyl substituted pyrimidines and triazines is also disclosed.

BACKGROUND OF THE INVENTION

[0001] This invention relates generally to novel para-tertiary alkylphenyl substituted triazines and pyrimidines and their use asprotectants against degradation by environmental forces, includingultraviolet light, actinic radiation, oxygen, moisture, atmosphericpollutants and combinations thereof.

[0002] Exposure to sunlight and other sources of ultraviolet radiationis known to cause degradation of a variety of materials, especiallypolymeric materials. For example, polymeric materials such as plasticsoften discolor and may become brittle as a result of exposure toultraviolet light. Accordingly, a large body of art has been developeddirected towards materials such as ultraviolet light absorbers andstabilizers which are capable of inhibiting such degradation.

[0003] A class of materials known to be ultraviolet light absorbers areo-hydroxyphenyltriazines, in which at least one substituent on the 1, 3or 5 carbon on the triazine ring is a phenyl group with a hydroxyl grouportho to the point of attachment to the triazine ring. In general thisclass of materials is well known in the art. Disclosures of suchcompounds can be found in U.S. Pat. Nos. 3,242,175 and 3,244,708.

[0004] A further example is found in U.S. Pat. Nos. 3,843,371 and3,896,125, which disclose various hydroxyphenyltriazines. Thesetriazines show poor solubilities and poor stabilities, and can discolorwith time.

[0005] Hydroxyphenyltriazines in combination with other UV absorberssuch as hydroxyphenylbenzotriazoles, benzophenones, oxanilides,cyanoacrylates, salicylates, acrylonitriles and thiozlines, are alsowell known. For example, U.S. Pat. Nos. 4,853,471, 4,973,702, 4,921,966and 4,973,701 disclose such combinations.

[0006] Typically, the aforementioned aryl ring with the hydroxyl grouportho to the point of attachment to the triazine ring is based onresorcinol and, consequently, this aryl ring also contains a secondsubstituent (either a hydroxyl group or a derivative thereof) para- tothe point of attachment to the triazine ring. For example, U.S. Pat.Nos. 3,118,837 and 3,244,708 disclose p-alkoxy-o-hydroxyphenyl triazineswith improved UV protection, but such triazines also exhibit poorsolubility and poor long-term stabilities.

[0007] This para-substituent can be “non-reactive,” as in the case of analkyloxy group, or “reactive” as in the case of a hydroxyalkyloxy(active hydrogen reactive site) or (meth)acryloyl (ethylenicunsaturation reactive site) group. For the purposes of the presentinvention, the former are referred to as “non-bondable”benzocycle-substituted pyrimidines and triazines and the latter arereferred to as “bondable” para-tertiary alkyl phenyl substitutedpyrimidines and triazines.

[0008] Many polymer additives (such as ultraviolet light stabilizers)volatilize or migrate out of the polymer substrate to be protected, orare adsorbed (chemically or physically) by one or more systemscomponents (such as pigments), thereby diminishing their effectiveness.Such volatilization, migration and adsorption problems are examples ofthe general problems of lack of solubility and compatibility found formany commercial polymer additives.

[0009] Bondable triazines are well known in the art. For example, U.S.Pat. Nos. 3,423,360, 4,962,142 and 5,189,084 disclose various bondableand the incorporation of these compounds into polymers by chemicalbonding. Bondable stabilizers have a potential advantage in this respectin that, depending on the bondable functionality and the particularpolymer system to be stabilized, they can be chemically incorporatedinto a polymer structure via reaction of the bondable functionalityeither during polymer formation (such as in the case of polymerizingmonomers or a crosslinking polymer system) or subsequently with apreformed polymer having appropriate reactive functionality. Due to suchbonding, migration of these UV absorbers between layers of multi-layercoatings and into polymer substrates is greatly reduced.

[0010] Several of the previously incorporated references disclosetertiary alkylated substituted triazines. For example U.S. Pat. Nos.3,242,175 and 3,244,708 disclose mono-tertiary butylated benzenetriazines. There remains a need for new UV-stabilizers which possessimproved compatibility with the polymer systems to which they are added,as well as impart improved environmental stability to such systems. Thepresent invention provides novel para-tertiary alkyl phenyl substitutedtriazine and pyrimidine stabilizers which satisfy this need.

SUMMARY OF THE INVENTION

[0011] The present invention provides a new class of para-tertiary alkylphenyl-substituted pyrimidines and triazines depicted below, in which asubstituent attached to the triazine or pyrimidine ring is a bondable ornon-bondable para-tertiary alkyl phenyl group:

[0012] wherein Z signifies a resorcinol radical which is bound through acyclic carbon atom directly to the triazine ring or a substitutedresorcinol radical, A can be a nitrogen or optionally substitutedmethine, and each R signifies a hydrocarbyl group to form a tertiarycarbon attached to the ring. These para-tertiary alkyl phenylsubstituted triazines and pyrimidines have the advantage of being highlysoluble in and compatible with many polymers and coatings while beingstable to environmental degradation that has lead previous UVstabilizers to turn yellow and to degrade with respect to performance asUV absorbers.

[0013] More specifically, the new para-tertiary alkyl phenyl substitutedpyrimidines and triazines of the present invention have general formula(II):

[0014] wherein

[0015] each A is independently nitrogen or methine optionallysubstituted with R², and at least two A are nitrogen;

[0016] X is independently selected from hydrogen and a blocking group

[0017] each of L, R³ and R⁴ are independently a hydrogen, hydrocarbyl,halogen, hydroxyl, cyano, —O(hydrocarbyl), —O(functional hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl), —N(functional hydrocarbyl)(functionalhydrocarbyl), —S(hydrocarbyl), —S(functional hydrocarbyl),—SO₂(hydrocarbyl), —SO₃(hydrocarbyl), —SO₂(functional hydrocarbyl),—SO₃(functional hydrocarbyl), —COO(hydrocarbyl), —COO(functionalhydrocarbyl), —CO(hydrocarbyl), —CO(functional hydrocarbyl),—OCO(hydrocarbyl), —OCO(functional hydrocarbyl), —CONH₂,—CONH(hydrocarbyl), —CONH(functional hydrocarbyl), —CON(hydrocarbyl)(hydrocarbyl), —CON(functional hydrocarbyl)(hydrocarbyl),—CON(functional hydrocarbyl)(functional hydrocarbyl), or a hydrocarbylgroup substituted by any of the above groups; and

[0018] each R is identical or different, and is independently ahydrocarbyl group of between 1 and 21 carbon atoms, an alkenyl group ofbetween 2 and 21 atoms, a cycloalkyl of between 5 and 21 carbon atoms,an aralkyl of between 7 and 21 carbon atoms, and of the abovehydrocarbyl groups substituted with one or more groups selected from thefollowing: halogen, hydroxyl, cyano, —O(hydrocarbyl), —O(functionalhydrocarbyl), —N(hydrocarbyl)(hydrocarbyl), —N(functionalhydrocarbyl)(functional hydrocarbyl), —S(hydrocarbyl), —S(functionalhydrocarbyl), —SO₂(hydrocarbyl), —SO₃(hydrocarbyl), —SO₂(functionalhydrocarbyl), —SO₃(functional hydrocarbyl), —COO(hydrocarbyl),—COO(functional hydrocarbyl), —CO(hydrocarbyl), —CO(functionalhydrocarbyl), —OCO(hydrocarbyl), —OCO(functional hydrocarbyl), —CONH₂,—CONH(hydrocarbyl), —CONH(functional hydrocarbyl),—CON(hydrocarbyl)(hydrocarbyl), —CON(functionalhydrocarbyl)(hydrocarbyl), —CON(functional hydrocarbyl)(functionalhydrocarbyl); provided that the R groups are connected to a quaternarycarbon that is attached to the ring.

[0019] Preferably L is hydrogen, a hydrocarbyl group of 1 to 24 carbonatoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms; and Ris methyl, ethyl, propyl or phenyl. It is more preferred that eachtertiary carbon attached to the ring have two R groups of methyl, ethylor propyl and one of phenyl, or all three R groups being methyl, ethylor propyl. It is most preferred for each tertiary carbon to have two Rgroups being methyl with the third R group being alkyl or phenyl. Morepreferably, each L in formula (II) is independently selected from thegroup consisting of:

[0020] hydrogen; an alkyl of 1 to 24 carbon atoms optionally substitutedby one or more hydroxyl, alkoxy, carboxy, carboalkoxy, amino, amido,carbamato, or epoxy groups, and which may contain one or more carbonylgroups, oxygen atoms or nitrogen atoms in the chain;

[0021] an alkenyl of 2 to 24 carbon atoms optionally substituted byhydroxyl, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, orepoxy groups and which may contain one or more carbonyl groups, oxygenatoms or nitrogen atoms in the chain;

[0022] an aralkyl of 7 to 24 carbon atoms optionally substituted by oneor more hydroxyl, alkoxy, chloro, cyano, carboxy, carboalkoxy, amino,amido, carbamato, or epoxy groups and may contain one or more carbonylgroups, oxygen atoms or nitrogen atoms in the ring;

[0023] a polyoxyalkylene radical of the formula XII

—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₁  (XII)

[0024] wherein D₁ is hydrogen,

[0025] —CH₂—CH(OH)—CH₂—OH, or R²⁵;

[0026] a polyoxyalkylene radical of the formula XIII

—CO(CH₂)_(u)—O—CH₂—(CH₂)_(u)—O—)_(mm)—D₂  (XIII)

[0027] wherein D₂ is —(CH₂)_(u)—CO—R²² or R²⁵;

[0028] a polyoxyalkylene radical of the formula VIII

—YY—O—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₃  (XIV)

[0029] wherein D₃ is —(CH₂)_(u)—CO—R²² or R²⁵;

[0030] a polyoxyalkylene radical of the formula XV

—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—B₁—D₄  (XV)

[0031] wherein D₄ is hydrogen of R²⁵;

[0032] a polyoxyalkylene radical of the formula XVI

—CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅  (XVI)

[0033] wherein D₅ is —NH₂, —NH—(CH₂)₂—COO—R²³ or —O—R²⁵;

[0034] a polyoxyalkylene radical of the formula XVII

—YY—O—CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅  (XVII)

[0035] wherein D₅ is as defined under formula (XVI);

[0036] a polyoxyalkylene radical of the formula XVIII

—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₆  (XVIII)

[0037] wherein D₆ is —NH—CO—R²⁴, —OR²⁵, OH or H;

[0038] a polyoxyalkylene radical of the formula XIX (XIX)

[0039] wherein D₇ is —OR²⁵, —NHCOR²⁴ or —OCH₂CH₂OR²⁵;

[0040] R²¹ is hydrogen or C₁-C₁₆ alkyl;

[0041] R²² is halogen or —O—R²³;

[0042] R²³ is hydrogen, C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, oraryl-C₁-C₄-alkyl;

[0043] R²⁴ is hydrogen, C₁-C₁₂ alkyl or aryl;

[0044] R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆ alkenyl, C₁-C₁₂alkylaryl or aryl-C₁-C₄ alkyl;

[0045] R²⁶ is hydrogen or C₁-C₄ alkyl;

[0046] R²⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy,halogen or aryl-C₁-C₄-alkyl;

[0047] R²⁸ and R²⁹ independently of one another are hydrogen, C₁-C₁₈alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy, or halogen;

[0048] R³⁰ is hydrogen, C₁-C₄ alkyl or CN;

[0049] YY is unsubstituted or substituted C₂-C₂₀ alkyl;

[0050] B₁ is HN or O;

[0051] kk is zero or an integer from 1-16;

[0052] mm is an integer from 2 to 60;

[0053] nn is an integer from 2 to 6;

[0054] u is an integer from 1 to 4;

[0055] and R is methyl.

[0056] The para-tertiary alkyl phenyl substituted pyrimidines andtriazines of the present invention further comprise oligomeric speciesof formulas (III), (IV) and (V):

[0057] wherein

[0058] A, R, R³, R⁴, and X, are as defined above;

[0059] r is an integer between 2 and 4;

[0060] D when r is 2, is selected from the group consisting of C₂-C₁₆alkylene, C₄-C₁₂ alkenylene, xylylene, C₄-C₂₀ alkylene which isinterrupted by one or more oxygen atoms, hydroxy-substituted C₃-C₂₀alkyl which is interrupted by one or more oxygen atoms,CH₂CH(OH)CH₂O—R¹⁵—OCH₂CH(OH)CH₂—, —CO—R₁₆—CO—, —CO—NH—R¹⁷—NH—CO—,—(CH₂)_(s)—COO—R¹⁸—OCO—(CH₂)_(s)—

[0061] a polyoxyalkylene bridge member of the formula XX

—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—CH₂—CH(OH)—CH₂—  (XX),

[0062] a polyoxyalkylene bridge member of the formula XXI

—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—  (XXI),

[0063] a polyoxyalkylene bridge member of the formula XXII

—YY—O—CO(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—COO—YY—  (XXII),

[0064] a polyoxyalkylene bridge member of the formula XXIII

—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)C_(nn)H_(2nn)—B₁—CO—CH(R²¹)—(CH₂)_(kk)—  (XXIII),

[0065] a polyoxyalkylene bridge member of the formula XXIV

—COCH(R²¹)CH₂NH(C_(nn)H_(2nn)O)_(mm)C_(nn)H_(2nn)—NHCH₂—CH(R²¹)CO—  (XXIV)

[0066] a polyoxyalkylene bridge member of the formula XXV

—YY—O—CO—(CH₂)₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—NH—(CH₂)₂COO—YY—  (XXV),

[0067] a polyoxyalkylene bridge member of the formula XXVI

—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—  (XXVI),

[0068] and a polyoxyalkylene bridge member of the formula XXVII

—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(a)—(O—CH₂—CH₂)_(b)—(O—CH₂—CH(CH₃)_(c)—  (XXVII),

[0069] wherein a+c=2.5 and b=8.5 to 40.5 or a+c=2 to 33 and b=0,

[0070] R²¹ is hydrogen or C₁-C₁₆ alkyl,

[0071] R²² is halogen or —O—R²³,

[0072] R²³ is hydrogen, C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, oraryl-C₁-C₄-alkyl,

[0073] R²⁴ is hydrogen, C₁-C₁₂ alkyl or aryl,

[0074] R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆ alkenyl, C₁-C₁₂alkylaryl or aryl-C₁-C₄ alkyl,

[0075] R²⁶ is hydrogen or C₁-C₄ alkyl,

[0076] R²⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy,halogen or aryl-C₁-C₄ alkyl,

[0077] R²⁸ and R²⁹ independently of one another are hydrogen, C₁-C₁₈alkyl, C₃-C₆ alkenyl, or C₁-C₁₈ alkoxy, or halogen;

[0078] R³⁰ is hydrogen, C₁-C₄ alkyl or CN,

[0079] YY is unsubstituted or substituted C₂-C₂₀ alkyl,

[0080] B₁ is NH or O;

[0081] kk is zero or an integer from 1-16,

[0082] mm is an integer from 2 to 60,

[0083] nn is an integer from 2 to 6,

[0084] u is an integer from 1 to 4;

[0085] when r is 3, D is

[0086] and when r is 4, D is

[0087] wherein R¹⁹ is C₃-C₁₀ alkanetriyl and R²⁰ is C₄-C₁₀ alkanetetryl;and

[0088] s is 1-6;

[0089] R¹⁵ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀dithiaalkylene, phenylene, naphthylene, diphenylene, or C₂-C₆alkenylene, or phenylene-XX-phenylene wherein XX is —O—, —S—, —SO₂—,—CH₂—, or —C(CH₃)₂—;

[0090] R¹⁶ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀dithiaalkylene, phenylene, naphthylene, diphenylene, or C₂-C₆ alkenyleneprovided that when r is 3 the alkenylene has at least 3 carbons;

[0091] R¹⁷ is C₂-C₁₀ alkylene, phenylene, naphthylene, diphenylene, orC₂-C₆ alkenylene, methylenediphenylene, or C₄-C₁₅ alkylphenylene; and

[0092] R¹⁸ is C₂-C₁₀ alkylene, or C₄-C₂₀ alkylene interrupted by one ormore oxygen atoms;

[0093] and

[0094] wherein

[0095] A, R, R³, R⁴, and L, are as defined above; r is 2 or 3;

[0096] X′, when r is 2, is —CO—R¹⁶—CO—, —CO₂—R¹⁶—CO₂—, —SO₂R¹⁶—SO₂—,—CO—NH—R¹⁷—NH—CO—, a polyoxyalkylene bridge member of formula—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—, or—COCH(R²¹)CH₂NH(C_(nn)H_(2nn)O)_(mm)C_(nn)H_(2nn)—NHCH₂—CH(R²¹)CO—

[0097] wherein R¹⁶ and R¹⁷ are as defined above.

[0098] and

[0099] wherein A, R³, L and X, are as defined above;

[0100] R⁴ is selected from the group consisting of straight chain alkylof 1 to 12 carbon atoms, branched chain alkyl of 1 to 12 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, alkyl substituted by cyclohexyl,alkyl interrupted by cyclohexyl, alkyl substituted by phenylene, alkylinterrupted by phenylene, benzylidene, —S—, —S—S—, —S—E—S—, —SO—, —SO₂—,—SO—E—SO—, —SO₂—E—SO₂—, —CH₂—NH—E—NH—CH₂—, and

[0101] wherein E is selected from the group consisting of alkyl of 2 to12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interruptedby cyclohexyl of 8 to 12 carbon atoms, alkyl terminated by cyclohexyl of8 to 12 carbon atoms; and

[0102] r is an integer between 2 and 4.

[0103] The para-tertiary alkyl phenyl substituted pyrimidines andtriazines of the present invention further comprise a compound offormula (XXXIV):

[0104] wherein

[0105] A, X, R, R³, and R⁴ are defined as in claim 1;

[0106] each of T and T′ is independently a direct bond, carbon, oxygen,nitrogen, sulfur, phosphorous, boron, silicon, or functional groupscontaining these elements;

[0107] each of Y and Z are each of Y, Z, R³ and R⁴ are independently ahydrogen, hydrocarbyl group, a functional hydrocarbyl group, halogen,hydroxyl, cyano, —O(hydrocarbyl), —O(functional hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl), —N(functional hydrocarbyl)(functionalhydrocarbyl), —N(hydrocarbyl)(functional hydrocarbyl), —S(hydrocarbyl),—S(functional hydrocarbyl), —SO₂(hydrocarbyl), —SO₂(hydrocarbyl),—SO₃(hydrocarbyl), —SO₃(functional hydrocarbyl), —COO(hydrocarbyl),—COO(functional hydrocarbyl), —CO(hydrocarbyl), —CO(functionalhydrocarbyl, —OCO(hydrocarbyl), —OCO(functional hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl), —CONH₂, —CONH(hydrocarbyl),—CONH(functional hydrocarbyl), —CON(hydrocarbyl)(hydrocarbyl),—CON(hydrocarbyl)(functional hydrocarbyl), —CON(functionalhydrocarbyl)(functional hydrocarbyl), —S(functional hydrocarbyl),—SO₂(functional hydrocarbyl), —SO₃(functional hydrocarbyl),—COO(functional hydrocarbyl), —CO(functional hydrocarbyl),—OCO(functional hydrocarbyl), or a hydrocarbyl group substituted by anyof the above groups.

[0108] The substituted pyrimidines and triazines of the presentinvention may optionally have the added benefit of being capable ofbeing chemically bonded to appropriate polymer systems via functionalityattached to the alkylphenyl, pyrimidine and triazine groups (e.g., by ahydroxyl, ethylenic unsaturated and/or activated unsaturated group inone or more of R¹, R², Y or Z).

[0109] These para-tertiary alkyl phenyl substituted pyrimidines andtriazines may in general be prepared via a number of procedures wellknown in the art, for example, those described in Brunetti, H; Luethi,C.; Helv. Chemica Acta, 55 (1972) pp. 1566-1595; Tanimoto, S.; Yamagata,M. Senryo to Yakahin, 40 (1995) pp 339ff, EP 779,280A1; Japanese PatentKokai Tokkyo Koho 9,059,263; and by Friedel-Crafts reaction startingwith a chloro-substituted triazine or pyrimidine.

[0110] The novel para-tertiary alkyl phenyl substituted pyrimidines andtriazines of the present invention are particularly useful asultraviolet light absorber agents for stabilizing a wide variety ofmaterials including, for example, organic compounds, oils, fats, waxes,cosmetics, dyes and biocides, and particularly various organic polymers(both crosslinked and non-crosslinked) used in applications such asphotographic materials, plastics, fibers or dyed fibers, rubbers, paintsand other coatings, and adhesives. The present invention, consequently,also relates to (1) a method of stabilizing a material which is subjectto degradation by actinic radiation (e.g., an organic material such asan organic polymer in the form of a film, fiber, shaped article orcoating) by incorporating into said material an amount of an actinicradiation stabilizer composition effective to stabilize the materialagainst the effects of actinic radiation, wherein the actinic radiationstabilizer composition comprises the inventive para-tertiary alkylphenyl substituted 1,3,5-triazine or pyrimidine; and (2) the material sostabilized.

[0111] The novel para-tertiary alkyl phenyl substituted pyrimidines andtriazines of the present invention are also effective as ultravioletlight screening agents in applications such as sunscreens and othercosmetic preparations, capstock layers for extruded polymers, dyedfibers and laminated UV-screening window films, among others. Thepresent invention, consequently, also relates (1) to a method ofprotecting a substrate against degradation by actinic radiation byapplying to the substrate an actinic radiation screening layer (e.g., acoating film or capstock layer) containing an actinic radiationscreening composition in an amount effective to reduce the amount ofactinic radiation impinging on the substrate, wherein the actinicradiation screening composition comprises the inventive para-tertiaryalkyl phenyl substituted pyrimidines and triazines; and (2) thesubstrate so protected.

[0112] The novel para-tertiary alkyl phenyl substituted pyrimidines andtriazines of the present invention may also be employed to form lightstabilizing compositions. Such light stabilizing compositions mayinclude a variety of other components known in the art including otherultraviolet light absorbers of the triazine class, other ultravioletlight absorbers of different classes (e.g. benzotriazoles,benzophenones), hindered amine light stabilizers, radical scavengers,antioxidants and the like.

[0113] These and other features and advantages of the present inventionwill be more readily understood by those of ordinary skill in the artfrom a reading of the following detailed description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0114] The para-tertiary alkyl phenyl substituted pyrimidines andtriazines

[0115] As used herein, the term “para-tertiary alkyl phenyl substitutedpyrimidines and triazines” broadly refers to any compound of formulas(I) through (V), above.

[0116] As used herein, the term “para-tertiary alkyl phenyl” broadlyrefers to any compound or substituent of general formula:

[0117] wherein substituent R is as above for general formulas (I)-(V);

[0118] The term “hydrocarbyl” in the context of the present invention,and in the above formulas, broadly refers to a monovalent hydrocarbongroup in which the valency is derived by abstraction of a hydrogen froma carbon atom. Hydrocarbyl includes, for example, aliphatics (straightand branched chain), cycloaliphatics, aromatics and mixed charactergroups (e.g., aralkyl and alkaryl). Hydrocarbyl also includes suchgroups with internal unsaturation and activated unsaturation. Morespecifically, hydrocarbyl includes (but is not limited to) such groupsas alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl andalkynyl, preferably having up to 24 carbon atoms. A hydrocarbyl mayoptionally contain a carbonyl group or groups (which is/are included inthe carbon count) and/or a heteroatom or heteroatoms (such as at leastone oxygen, sulfur, nitrogen or silicon), in the chain or ring.

[0119] The term “functional hydrocarbyl” in the context of the presentinvention, and in the above formulas, broadly refers to a hydrocarbylpossessing pendant and/or terminal reactive and/or latent reactivefunctionality and/or leaving groups. “Reactive” functionality refers tofunctionality which is reactive with common monomer/polymerfunctionality under normal conditions well understood by those personsof ordinary skill in the relevant art. As non-limiting examples ofreactive functionality may be mentioned active hydrogen containinggroups such as hydroxyl, amino, carboxyl, thio, amido, carbamoyl andactivated methylene; isocyanato; cyano; epoxy; ethylenically unsaturatedgroups such as allyl and methallyl; and activated unsaturated groupssuch acryloyl and methacryloyl, and maleate and maleimido (including theDiels-Alder adducts thereof with dienes such as butadiene). “Latentreactive” functionality within the meaning of the present invention and,as would clearly be understood by those persons of ordinary skill in theart, refers to reactive functionality which is blocked or masked toprevent premature reaction. As examples of latent reactive functionalitymay be mentioned ketimines and aldimines (amines blocked, respectively,with ketones and aldehydes); amine-carboxylate salts; and blockedisocyanates such as alcohol (carbamates), oxime and caprolactam blockedvariations. A “leaving” group within the meaning of the presentinvention, as would clearly be understood by those persons of ordinaryskill in the relevant art, is a substituent attached to the hydrocarbylchain or ring which during reaction is dislodged or displaced to createa valency on a carbon or hetero atom in the hydrocarbyl chain or ring,said valency being filled by a nucleophile. As examples of leavinggroups may be mentioned halogen atoms such as chlorine, bromine andiodine; hydroxyl groups (protonated and unprotonated); quaternaryammonium salts (NT₄ ⁺); sulfonium salts (ST₃ ⁺); and sulfonates(—OSO₃T); where T is, e.g., methyl or para-tolyl. Of all these classesof reactive functionality, the preferred functionality includeshydroxyl, —COOR⁵, —CR⁶═CH₂, —CO—CR⁶═CH₂, Cl, an isocyanate group, ablocked isocyanate group and —NHR⁵, wherein

[0120] R⁵ is selected from hydrogen and a hydrocarbyl (preferably of upto 24 carbon atoms); and

[0121] R⁶ is selected from hydrogen and an alkyl of 1 to 4 carbon atoms(preferably hydrogen and methyl).

[0122] The term “hydrocarbylene” in the context of the present inventionis a divalent hydrocarbon group in which both valencies derive byabstraction of hydrogens from carbon atoms. Included within thedefinition of hydrocarbylene are the same groups as indicated above forhydrocarbyl and functional hydrocarbyl with, of course, the extravalency (for example, alkylene, alkenylene, arylene, alkylaryl, etc.).

[0123] The term “functional hydrocarbylene” in the context of thepresent invention refers to a species of hydrocarbylene possessingpendant reactive functionality, latent reactive functionality and/orleaving groups. The term “non-functional hydrocarbylene” in the contextof the present invention refers generally to a hydrocarbylene other thana functional hydrocarbylene.

[0124] The para-tertiary alkyl phenyl substituted pyrimidines andtriazines in accordance with the present invention also relate to latentstabilizing compounds against actinic radiation of the general formulas(I)-(V), wherein at least one of the hydroxyl groups on the aryl ringortho to the point of attachment to the triazine or pyrimidine ring isblocked, that is, wherein at least one X is other than hydrogen. Suchlatent stabilizing compounds liberate the effective stabilizers bycleavage of the O—X bond, e.g., by heating or by exposure to UVradiation. Latent stabilizing compounds are desirable because they havemany favorable properties, i.e., good substrate compatibility, goodcolor properties, a high cleavage rate of the O—X bond and a long shelflife. The use of latent stabilizing compounds is further described inU.S. Pat. Nos. 4,775,707, 5,030,731, 5,563,224 and 5,597,854, which areincorporated herein for all purposes as if fully set forth.

[0125] Latent stabilizing compounds comprising the para-tertiary alkylphenyl substituted pyrimidines and triazines in accordance with thepresent invention can be prepared from compounds of the general formulas(I)-(V), wherein at least one X is hydrogen, by subjecting saidcompounds to a further reaction to form latent stabilizing compounds, asdescribed in the immediately preceding incorporated references.

[0126] As preferred examples of blocking groups X may be mentioned oneor more of the following groups: allyl, —COR^(a), —SO₂R^(b),—SiR^(c)R^(d)R^(e), —PR^(f)R^(g) or —POR^(f)R^(g), —CONHR^(h), wherein

[0127] each R^(a) is independently selected from C₁-C₈ alkyl,halogen-substituted C₁-C₈ alkyl, C₅-C₁₂ cycloalkyl, C₂-C₈ alkenyl,—CH₂—CO—CH₃, C₁-C₁₂ alkoxy, and phenyl or phenoxy which is unsubstitutedor substituted by C₁-C₁₂ alkyl, C₁-C₄ alkoxy, halogen and/or benzyl;

[0128] each R^(b) is independently selected from C₁-C₁₂ alkyl, C₆-C₁₀aryl and C₇-C₁₈ alkylaryl;

[0129] each R^(c), R^(d) and R^(e) is independently selected from C₁-C₁₈alkyl, cyclohexyl, phenyl and C₁-C₁₈ alkoxy;

[0130] each R^(f) and R^(g) is independently selected from C₁-C₁₂alkoxy, C₁-C₁₂ alkyl, C₅-C₁₂ cycloalkyl, and phenyl or phenoxy which isunsubstituted or substituted by C₁-C₁₂ alkyl, C₁-C₄ alkoxy, halogenand/or benzyl; and

[0131] each R^(h) is independently selected from C₁-C₈ alkyl, C₅-C₁₂cycloalkyl, C₂-C₈ alkenyl, —CH₂—CO—CH₃, and phenyl which isunsubstituted or substituted by C₁-C₁₂ alkyl, C₂-C₈ alkenyl, C₁-C₄alkoxy, halogen and/or benzyl.

[0132] The reaction to give the latent stabilizing compounds of thepresent invention of the general formula (I) and (II), in which X isallyl, —COR^(a), —SO₂R^(b), —SiR^(c)R^(d)R^(e), —PR^(f)R^(g) or—POR^(f)R^(g), can be carried out, for example, by reaction of thecompounds of the general formula (III) through (V), wherein at least oneX is hydrogen with the corresponding halides such as allyl chloride,Cl—COR^(a), Cl—SO₂R^(b), Cl—SiR^(c)R^(d)R^(e), Cl—PR^(f)R^(g), orCl—POR^(f)R^(g). The reaction to give the latent stabilizing compoundsof the present invention of the general formulas (III) through (V) inwhich X is —CONHR^(h) can be carried out, for example, by reaction ofthe compounds of the general formulas (III) through (V), wherein atleast one X is hydrogen with the corresponding isocyanates. Furthermore,acylated compounds can be obtained by reaction with anhydrides, ketenesor esters, such as lower alkyl esters, as is well known to one skilledin the art. The above-described reagents may be used in approximatelyequimolar amounts or in excess, for example, from 2 to 20 mol withrespect to the hydroxyl groups desired to be made latent in the startingcompound of the general formula (I) or (II).

[0133] Catalysts customarily used for acylation, sulfonylation,phosphonylation, silylation or urethanation reactions may be used informing the latent stabilizing substituted pyrimidines and triazines ofthe present invention. For example, acylation and sulfonylation reactioncatalysts such as tertiary or quaternary amines, such as triethylamine,dimethylaminopyridine or tetrabutylammonium salts, may be used forforming these latent stabilizing compounds.

[0134] The reaction may be carried out in the presence of a solvent,such as relatively inert organics, e.g., hydrocarbons such as tolueneand xylene, chlorinated hydrocarbons such as carbon tetrachloride orchloroform, or ethers such as tetrahydrofuran or dibutyl ether, orwithout a solvent. Alternatively, the reagent(s) may be employed as thesolvent. The reaction temperature is usually between room temperatureand about 150° C., for example, up to the boiling point of the solventwhen a solvent is used.

[0135] In preferred embodiments, each X is hydrogen.

[0136] In preferred embodiments, L is selected from the group consistingof hydrogen, C₁-C₂₄ alkyl or mixtures thereof; C₁-C₂₄ branched alkyl ormixtures thereof, C₃-C₆ alkenyl; —COR¹²; —COOR¹²; —CONHR¹²; —SO₂R¹³;C₁-C₁₈ alkyl which is substituted with one or more of the groups:

[0137] hydroxy, C₁-C₁₈ alkoxy, C₃-C₁₈ alkenoxy, halogen, phenoxy, C₁-C₁₈alkyl-substituted phenoxy, C₁-C₁₈ alkoxy-substituted phenoxy,halogen-substituted phenoxy, —COOH, —COOR⁹, CONH₂, —CONHR⁹,—CON(R⁹)(R¹⁰), —NH₂, —NHR⁹, —N(R⁹)(R¹⁰), —NHCOR¹¹, N(R⁹)COR¹¹,—NHCOOR¹¹, —N(R⁹)COOR¹¹, —CN, —OCOR¹¹, —OC(O)NHR⁹, —OC(O)N(R⁹)(R¹⁰),C₂-C₅₀ alkyl which is interrupted by one or more oxygen atoms orcarbonyl groups and optionally substituted by one or more substituentsselected from the group consisting of hydroxy, C₁-C₁₂ alkoxy, andglycidyloxy; glycidyl; and cyclohexyl optionally substituted withhydroxyl or —OCOR¹¹.

[0138] R⁹ and R¹⁰ independently of one another are C₁-C₁₂ alkyl, C₃-C₁₂alkoxyalkyl, C₄-C₁₆ dialkylaminoalkyl, or C₅-C₁₂ cycloalkyl, or R⁹ andR¹⁰ taken together are C₃-C₉ alkylene or C₃-C₉ oxoalkylene or C₃-C₉azaalkylene.

[0139] R¹¹ is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, or phenyl.

[0140] R¹² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, phenyl, C₁-C₁₂ alkoxy,phenoxy, C₁-C₁₂ alkylamino; phenylamino, tolylamino or naphthylamino andR¹³ is C₁-C₁₂ alkyl, phenyl, naphthyl or C₇-C₁₄ alkylphenyl.

[0141] Some of these groups as well as others are described in U.S. Pat.Nos. 5,106,891, 5,189,084, 5,356,995, 5,637,706, 5,726,309, EP 434,608,EP 704,437, WO 96/28431, and GB 2,293,823 which are incorporated hereinby reference for all purposes as if fully set forth.

[0142] L may also be an alkyl of 1-24 carbon atoms substituted by ahindered amine light atabilizer (HALS) of the general formula (VI).Triazines containing tetramethylpiperidine groups are described in U.S.Pat. Nos. 4,161,592 and 5,376,710 which are incorporated herein byreference for all purposes as if fully set forth.

[0143] wherein

[0144] J is —O—, —NR³⁰, —T—(CH2)2—NR³⁰— wherein T is —O— or —S—, and

[0145] R³⁰ is C₁-C₁₂ alkyl or hydrogen;

[0146] R³¹ is hydrogen or C₁-C₈ alkyl;

[0147] R³² is hydrogen, oxygen, C₁-C₂₁ alkoxyalkyl, C₇-C₈ aralkyl,2,3-epoxypropyl, and aliphatic acyl group with 1-4 C atoms or one of thegroups —CH₂COOR³³, —CH₂—CH(R³⁴)—OR³⁵, —COOR³⁶ or —CONHR³⁶, wherein R³³is C₁-C₁₂ alkyl, C₃-C₆ alkenyl, phenyl, C₇-C₈ aralkyl or cyclohexyl, R³⁴is a hydrogen, methyl or phenyl, R³⁵ is hydrogen, an aliphatic,aromatic, araliphatic or alicyclic acyl group with 1-8 C atoms, whereinthe aromatic part is unsubstituted or is substituted by chlorine, C₁C₄alkyl, C₁-C₈ alkoxy or by hydroxyl, and R³⁶ is C₁-C₁₂ alkyl, cyclohexyl,phenyl or benzyl;

[0148] R³⁷ is hydrogen, —OH or one of the groups —O—CO—R³⁸ or—NR³⁶—CO—R³⁸, wherein R³⁸ is C₁-C₁₂ alkyl or phenyl; and

[0149] K is —O—(C_(mm)H_(2mm))— wherein mm is 1 to 6,

[0150] Most preferably, each L group is independently selected fromhydrogen, an alkyl of 1 to 24 carbon atoms, or mixtures thereof; analkyl of 4 to 20 carbon atoms containing one or more oxygen atoms in thechain and optionally substituted with one or more hydroxyl groups, ormixtures thereof.

[0151] In preferred embodiments, each R³ and R⁴ is independentlyselected from hydrogen, halogen, a hydrocarbyl group of 1 to 24 carbonatoms, a hydrocarbyloxy group of 1 to 24 carbon atoms, an acyl group of2 to 24 carbon atoms, an acyloxy group of 2 to 24 carbon atoms and —OR.More preferably, each R³ and R⁴ is independently selected from hydrogen,an alkyl of 1 to 24 carbon atoms optionally containing an oxygen atom inthe chain; an alkyloxy of 1 to 24 carbon atoms; an alkenyl of 2 to 24carbon atoms (which may optionally be substituted by hydroxyl, carboxyland/or amino group(s) and/or contain carbonyl, oxygen and/or nitrogen inthe chain); an alkenyloxy of 2 to 24 carbon atoms (which may optionallybe substituted by hydroxyl, carboxyl and/or amino group(s) and/orcontain carbonyl, oxygen and/or nitrogen in the chain); a cycloalkyl of5 to 12 carbon atoms (which may optionally be substituted by hydroxyl,carboxyl and/or amino group(s) and/or contain carbonyl, oxygen and/ornitrogen in the ring); an acyl group of 2 to 12 carbon atoms; optionallysubstituted benzoyl and —OR. Still more preferably, each R³ and R⁴ isindependently selected from hydrogen, an alkyl of 1 to 24 carbon atomsoptionally containing an oxygen atom in the chain, an alkyloxy of 1 to 8carbon atoms optionally containing an oxygen atom in the chain, ahydroxyalkyl of 1 to 24 carbon atoms group optionally containing anoxygen atom in the chain, a hydroxyalkyloxy of 1 to 8 carbon atoms groupoptionally containing an oxygen atom in the chain, an acyl group of 2 to12 carbon atoms, an acyloxy of 2 to 12 carbon atoms and —OR. Especiallypreferred is when each R³ and R⁴ is independently selected fromhydrogen, an alkyl of 1 to 4 carbon atoms and —OR, and particularlyhydrogen and methyl.

[0152] In another preferred embodiment, R³ and R⁴ are independentlymethylene or alkylidene substituted by a benzophenone UV absorber or abenzotriazole UV absorber. Related triazine Obenzotriazole andtriazine-benzophenone hybrid UV absorbers are disclosed in U.S. Pat. No.5,585,422 which is incorporated by reference herein for all purposes asif fully set forth. In a related preferred embodiment, R³ and R⁴ areindependently methylene, alkylidene, or benzylidene substituted by asecond UV absorber. Related triazine dimers (and oligomers) aredisclosed in U.S. Pat. No. 5,726,309 and EP 704,437 which areincorporated by reference herein for all purposes as if fully set forth.

[0153] In preferred embodiments, each of R³ and R⁴ is independentlyselected from hydrogen, halogen, acyl of 2 to 24 carbon atoms, benzoyland substituted benzoyl, alkyl having from 1 to 24 carbon atoms, alkenylof 2 to 24 carbon atoms, cycloalkyl of 5 to 24 carbon atoms and aralkylof 7 to 24 carbon atoms.

[0154] Further preferred embodiments may include any combination of theparameters mentioned above.

[0155] Methods of Preparation

[0156] The novel alkyated para-tertiary alkyl phenyl substitutedpyrimidines and triazines of the present invention can be preparedthrough the Friedel-Crafts reaction of an aromatic moiety (XXX) with ahalogen-substituted pyrimidine or triazine compound of Formula (XXXI).

[0157] The term “Lewis acid” is intended to include aluminum halides,alkylaluminum halides, boron halides, tin halides, titanium halides,lead halides, zinc halides, iron halides, gallium halides, arsenichalide, copper halides, cadmium halides, mercury halides, antimonyhalides, and the like. Preferred Lewis acids include aluminumtrichloride, aluminum tribromide, trimethylaluminum, boron trifluoride,boron trichloride, zinc dichloride, titanium tetrachloride, tindichloride, tin tetrachloride, or a mixture thereof.

[0158] As used herein, the term “acid” includes any inorganic or organicacid with at least one acidic proton, which may or may not be dissolvedin an aqueous or organic solution. The organic acids include any organiccompound that contains at least one acidic functional group includingRCO₂H, RSO₃H, RSO₂H, RSH, ROH, RPO₃H, RPO₂H, wherein R is as definedabove. Preferred protic acids include HCl, HBr, HI, HNO₃, HNO₂, H₂S,H₂SO₄, H₃PO₄, H₂CO₃, acetic acid, formic acid, propionic acid, butanoicacid, benzoic acid, phthalic acid, oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, methanesulfonic acid, andp-toluenesulfonic acid or mixtures thereof.

[0159] As used herein, the term “step-wise” means a reaction sequencewherein a series of reactions are conducted, the first reactionproducing compounds of Formula (XXXII) and being carried out to betweenabout 50% to about 100% completion prior to addition of a compound ofFormula (XXXIII) to produce compounds of Formula (II). Preferably thereaction is carried out to between about 70% to about 100% completionprior to addition of compound of Formula (XXXIII), and more preferablyto between about 75% to about 100% completion.

[0160] As used herein, the term “continuous” means a reaction sequencenot defined as “step-wise.”

[0161] The novel alkyated para-tertiary alkyl phenyl substitutedpyrimidines and triazines of the present invention can be preparedthrough the Friedel-Crafts reaction of an aromatic moiety (XXX) with ahalogen-substituted pyrimidine or triazine compound of Formula (XXXI).See Scheme 1.

[0162] wherein Hal is bromine, chlorine, or iodine. Compound (XXX) isdefined as a benzene molecule wherein one hydrogen is substituted with atertiary alkyl group, and tertiary alkyl group is as defined above. Incompound (XXXI) Hal, is a halogen, preferably bromine, chlorine, oriodine, and A is as defined above. In compound (XXXIII) L, X, R³, and R⁴are as defined above. Substitution of either L or X, or both for analkyl group or hydroxy blocking group can be conducted before or afterthe second step. One of ordinary skill in the art with little or noexperimentation can easily determine the conditions to substitute eitherL or X, or both.

[0163] The relative amounts of the reactants are as follows. The amountof compounds of Formula (XXXI) should be in sufficient amounts to reactwith aromatic compounds of Formula (XXX) to produce compounds of Formula(XXXII). The amount of aromatic compound of Formula (XXX) is importantto ensure that a sufficient amount of aromatic compounds of Formula(XXXII) is synthesized without excessive amounts of undesired sideproducts such as trisaryl triazine or trisaryl pyrimidine. Moreover,excess amounts of aromatic compounds can lead to undesired productdistributions enriched in mono- and tris-aryl triazines, or mono- andtris-aryl pyrimidines thus, making product separation and purificationdifficult and resource consuming.

[0164] The amount of aromatic compounds (XXX) should be in sufficientamounts to synthesize 2-halo-4,6-bisaryl-1,3,5-triazine or2-halo-4,6-bisarylpyrimidine. Preferably, there should be between about1 to about 5 mol equivalents of aromatic compound of Formula (XXX) tocompound of Formula (XXXI). The amount of aromatic compound of Formula(XXXIII) should be between about 0.5 to about 2.5 mol equivalents ofaromatic compound of Formula (XXXIII) to compounds of Formula (XXXII).The amount of Lewis acid, Al(Hal)₃ wherein Hal is a halide as definedabove, used in the reaction should be in sufficient amounts to transform2,4,6-trihalo-1,3,5-triazine or 2,4,6-trihalo-pyrimidine to thepreferred 2-halo-4,6-bisaryl-1,3,5-triazine or2-halo-4,6-bisarylpyrimidine, respectively. The amount of Lewis acidshould be between about 0.5 to about 500 mol equivalents. Preferably,the amount of Lewis acid should be between about 1 to about 5 molequivalents.

[0165] Advantageously, an acid can be used in conjunction with a Lewisacid when synthesizing compounds of Formula (II) or (XXXII). The amountof acid used in the reaction should be in sufficient amounts totransform 2,4,6-trihalo- 1,3,5-triazine or 2,4,6-trihalopyrimidine tothe preferred 2-halo-4,6-bisaryl-1,3,5-triazine or2-halo-4,6-bisarylpyrimidine, respectively, or convert2-halo-4,6-bisaryl-1,3,5-triazine or 2-halo-4,6-bisarylpyrimidine to thecompounds of Formula (II), as desired. Preferably, the amount of acidshould be between about 0.01 mol to about 5 mol equivalents.

[0166] For synthetic scheme 1, the Lewis acid and acid preferablycombine to form a mixture that can be prepared in situ or preformedprior to addition to the reagents. The Lewis acid and/or acid can becombined with either aromatic compounds of Formula (XXX), compounds ofFormula (XXXI), or both, in any manner. In situ reaction mixturepreparation comprises addition of at least one Lewis acid and at leastone acid to at least one compound of Formula (XXXI), at least onearomatic compound of Formula (XXX), and optionally solvent, withoutregard to addition order. To prepare the mixture prior to addition tothe reagents, i.e., the preformed method, at least one Lewis acid and atleast one acid are combined and allowed to mix prior to addition,optionally in an inert solvent. Thereafter, the mixture is added to thereagents or vice versa, as desired and in any addition order. As usedherein, one or more Lewis acids may be used, the first step and thesecond step Lewis acid may be the same or different. Additionally, oneor more acids may be used, the first step and second step acid may bethe same or different. In the “continuous” process, the use ofadditional Lewis acid, acid, or both is optional.

[0167] If the complex is prepared using the pre-formed method, preferredmixing time of the Lewis acid and acid, prior to addition to thereagents, is between about 1 minute to about 5 hours, more preferredtime is between about 10 minutes to about 2 hours. The preferred mixingtemperature of the Lewis acid and acid mixture, prior to addition to thereagents, is between about −50° C. to about 100° C., more preferred isbetween about −10° C. to about −50° C.

[0168] The reaction should run for a sufficient amount of time, at asufficient temperature and pressure to synthesize the desired triazineor pyrimidine compound. The preferred reaction time for the synthesis ofcompounds of Formula (XXXII), i.e., the first step, is between about 5minutes and about 48 hours, more preferred between about 15 minutes andabout 24 hours. The preferred reaction time for the synthesis ofcompounds of Formula (II), i.e., the second step, is between about 10minutes and about 24 hours, more preferably time is between about 30minutes and about 12 hours. The preferred reaction temperature for thefirst step is between about −50° C. and about 150° C., more preferredreaction temperature between about −30° C. and about 50° C. The reactionpressure is not critical and can be about 1 atm or higher if desired.Preferably, the reaction is carried out under an inert gas such asnitrogen or argon. The preferred reaction temperature for the secondstep is between about 0° C. and about 120° C., a more preferred reactiontemperature is between about 20° C. and about 100° C.

[0169] The step-wise process comprises mixing at least one Lewis acid,at least one acid, and compounds of Formula (XXXI) with one or more ofthe desired aromatic compounds of Formula (XXX), preferably until thereaction is between about 70% to about 100% completed. Thereafter, theproduct is isolated and purified. The aromatic compound of Formula(XXXIII) is added to the purified product along with Lewis acid andoptionally an acid to synthesize the compounds of Formula (II). Thestep-wise sequence allows for the isolation, purification, and storageof compounds of Formula (XXXII) prior to subsequent reaction witharomatic compounds of Formula (XXXIII).

[0170] The continuous reaction comprises allowing a compound of Formula(XXXI) to react with one or more aromatic compounds of Formula (XXX) inthe presence of at least one Lewis acid and at least one acid preferablyuntil the reaction is between about 70% to about 100% complete.Thereafter, without isolating the product of Formula (XXXII), thearomatic compound of Formula (XXXIII) is allowed to react with theproduct of Formula (XXXII) in the presence of optionally at least onesecond Lewis acid and optionally at least one second acid preferablyuntil the reaction is between about 70% to about 100% complete. Thecontinuous reaction eliminates the need to purify the intermediateproduct of Formula (XXXII) or use of additional reagents such assolvents, and optionally Lewis acids and acids. Moreover, the one-stepprocess simplifies the synthetic reaction pathway such that nounnecessary handling or processing of the reaction mixture is requireduntil the reaction is completed.

[0171] To synthesize compounds of Formulas (II) or (XXXII) using thepre-formed method, the preferred addition time of the Lewis acid/acidmixture to a reagent mixture is between about 5 minutes to about 5hours, more preferred time is between about 15 minutes to about 3 hours.The addition temperature of the Lewis acid/acid mixture to a reagentmixture is between about −50° C. to about 150° C., preferred additiontemperature is between about −30° C. to about 50° C., and more preferredaddition temperature is between about −20° C. to about 80° C.

[0172] To synthesize compounds of Formulas (II) or (XXXII) using thepre-formed method, the preferred addition temperature of the Lewisacid/acid mixture is between about 0° C. to about 100° C., preferredaddition temperature is between about 20° C. to about 80° C.

[0173] To synthesize compounds of Formula (II) the preferred additiontime of the aromatic compound of Formula (XXXIII) to the reactionmixture is between about 5 minutes to about 10 hours, more preferredaddition time is between about 10 minutes to about 5 hours, and mostpreferred addition time is between about 15 minutes to about 2 hours.The addition temperature of the aromatic compound of Formula (XXXIII) tothe reaction mixture is between about 0° C. to about 150° C., preferredaddition temperature is between about 20° C. to about 100° C.

[0174] The Lewis acid/acid mixture should be present in amountssufficient to react with the number of halogens being substituted oncompounds of Formula (XXXI). A range of between about 1 to about 5 molequivalents of Lewis acid and a range of between about 0.01 mol to about5 mol equivalents of acid can be used. The preferred Lewis acid isaluminum chloride. A preferred amount of Lewis acid is between about 2to about 4 mol equivalents to halo-triazine or halo-pyrimidine. Apreferred amount of acid is between about 0.05 mol to about 2 molequivalents to compounds of Formula (XXXI).

[0175] The synthesis of compounds of Formula (III), (IV), or (V) can beperformed by methods commonly known in the art. One of ordinary skill inthe art with little or no experimentation can determine the appropriateconditions to obtain the polymer product desired.

[0176] Other useful methods of synthesis of substituted triazines aredisclosed in the following sources: U.S. Pat. Nos. 5,106,972, 5,438,138,5,478,935, WO 96/28431, EP 649841, EP 648756, EP 577559, Brunetti, H;Luethi, C.; Helv. Chemica Acta, 55 (1972) pp. 1566-1595; Tanimoto, S.;Yamagata, M. Senryo to Yakahin, 40 (1995) pp 339ff; EP 779,280A1; andJapanese Patent Kokai Tokkyo Koho 9,059,263.

[0177] Uses of the para-tertiary alkyl phenyl substituted pyrimidinesand triazines

[0178] As indicated earlier, the novel para-tertiary alkyl phenylsubstituted pyrimidines and triazines of the present invention areparticularly useful as ultraviolet light absorber agents for stabilizinga wide variety of materials including, for example, various polymers(both crosslinked and thermoplastic), photographic materials and dyesolutions for textile materials, as well as in ultraviolet lightscreening agents (such as sunscreens). The novel para-tertiary alkylphenyl substituted pyrimidines and triazines of the present inventioncan be incorporated into such material in any one of a variety ofconventional manners, including for example, physical mixing orblending, optionally, with chemical bonding to the material (typicallyto a polymer), as a component in a light stabilizing composition such asa coating or solution, or as a component in a UV screening compositionsuch as a sunscreen composition.

[0179] In one embodiment of the present invention, the para-tertiaryalkyl phenyl substituted pyrimidines and triazines of the presentinvention can be employed to stabilize materials which are subject todegradation by ultraviolet radiation by incorporating the presentlyclaimed compounds into polymeric materials, either chemically orphysically. Non-limiting examples of polymeric materials that may be sostabilized are polyolefins, polyesters, polyethers, polyketones,polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes,high-impact polystyrenes, polyacrylates, polymethacrylates, polyacetals,polyacrylonitriles, polybutadienes, polystyrenes, ABS, SAN (styreneacrylonitrile), ASA (acrylate styrene acrylonitrile), cellulosic acetatebutyrate, cellulosic polymers, polyimides, polyamideimides,polyetherimides, polyphenylsulfides, PPO, polysulfones,polyethersulfones, polyvinylchlorides, polycarbonates, polyketones,aliphatic polyketones, thermoplastic TPU's, aminoresin crosslinkedpolyacrylates and polyesters, polyisocyanate crosslinked polyesters andpolyacrylates, phenol/formaldehyde, urea/formaldehyde andmelamine/formaldehyde resins, drying and non-drying alkyd resins, alkydresins, polyester resins, acrylate resins cross-linked with melamineresins, urea resins, isocyanates, isocyanurates, carbamates, and epoxyresins, cross-linked epoxy resins derived from aliphatic,cycloaliphatic, heterocyclic and aromatic glycidyl compounds, which arecross-linked with anhydrides or amines, polysiloxanes, Michael additionpolymers, amines, blocked amines with activated unsaturated andmethylene compounds, ketimines with activated unsaturated and methylenecompounds, polyketimines in combination with unsaturated acrylicpolyacetoacetate resins, polyketimines in combination with unsaturatedacrylic resins, radiation curable compositions, epoxymelamine resins,organic dyes, cosmetic products, cellulose-based paper formulations,photographic film paper, ink, and blends thereof.

[0180] Further non-limiting examples of specific polymers which may bestabilized include:

[0181] 1. Homo- and copolymers of monoolefins and diolefins includingbut not limited to ethylene, propylene, isobutylene, butene,methylpentene, hexene, heptene, octene, isoprene, butadiene, hexadiene,dicyclopentadiene, ethylidene and cycloolefins such as cyclopentene andnorbomene; for example, polyethylenes (which optionally can becrosslinked) such as high density polyethylene (HDPE), high density andhigh molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE) and branched low density polyethylene (BLDPE).

[0182] 2. Copolymers of one or more monoolefins and/or diolefins withcarbon monoxide and/or with other vinyl monomers, including limitedacrylic and methacrylic acid, acrylates and methacrylates, acrylamides,acrylonitriles, styrenes, vinyl acetate (such as ethylene/vinyl acetatecopolymers), vinyl halides, vinylidene halides, maleic anhydride andallyl monomers such as allyl alcohol, allyl amine ally glycidyl etherand derivatives thereof.

[0183] 3. Hydrocarbon resins (such as C₅-C₉) including hydrogenatedmodifications thereof and mixtures of polyalkylenes and starch.

[0184] 4. Homo- and copolymers of styrenes such as styrene,p-methylstyrene and α-methylstyrene.

[0185] 5. Copolymers of one or more styrenes with other vinyl monomerssuch as olefins and diolefins (e.g., ethylene, isoprene and/orbutadiene), acrylic and methacrylic acid, acrylates and methacrylates,acrylamides, acrylonitriles, vinyl acetate (such as ethylene/vinylacetate copolymers), vinyl halides, vinylidene halides, maleic anhydrideand allyl compounds such as allyl alcohol, allyl amine allyl glycidylether and derivatives thereof.

[0186] 6. Graft copolymers of styrenes on polybutadienes,polybutadiene/styrene copolymers and polybutadiene/acrylonitrilecopolymers; styrene (or α-methylstyrene) and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and acrylonitrile on ethylene/propylene/dienecopolymers; styrene and acrylonitrile on polyalkyl acrylates ormethacrylates; and styrene and acrylonitrile on acrylate/butadienecopolymers.

[0187] 7. Halogen-containing polymers such as polychloroprene;chlorinated rubbers; chlorinated and brominated isobutylene/isoprenecopolymers; chlorinated or sulfochlorinated polyethylene; copolymers ofethylene and chlorinated ethylene; epichlorohydrin polymers andcopolymers; and polymers and copolymers of halogen-containing vinylcompounds such as vinyl chloride, vinylidene chloride, vinyl fluorideand/or vinylidene fluoride and other vinyl monomers.

[0188] 8. Homo- and copolymers derived from α,β-unsaturated acids andderivatives thereof such as acrylic acid, methacrylic acid, acrylates,methacrylates, acrylamides and acrylonitriles.

[0189] 9. Copolymers of the monomers mentioned in (8) with otherunsaturated monomers such as olefins and diolefins (e.g., butadiene),styrenes, vinyl halides, maleic anhydride and allyl monomer such asallyl alcohol, allyl amine, allyl glycidyl ether and derivativesthereof.

[0190] 10. Homo- and copolymers derived from unsaturated alcohols andamines or the acyl derivatives or acetals thereof, such as vinylalcohol, vinyl acetate, vinyl stearate, vinyl benzoate, vinyl maleate,vinyl butyral, allyl alcohol, allyl amine, allyl glycidyl ether, allylphthalate and allyl melamine; as well as copolymers of such monomerswith other ethylenically unsaturated monomers mentioned above.

[0191] For the preceding groups 1-10 of polymers, the present inventionfurther encompasses these polymers as prepared by metallocene catalysts.

[0192] 11. Homo- and copolymers of cyclic ethers such as alkyleneglycols and alkylene oxides, as well as copolymers with bisglycidylethers.

[0193] 12. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain ethylene oxide as a comonomer; andpolyoxymethylenes modified with thermoplastic polyurethanes, acrylatesand/or MBS.

[0194] 13. Polyphenylene oxides and sulfides.

[0195] 14. Polyurethanes derived from hydroxy-functional components suchas polyhydric alcohols, polyethers, polyesters, polyacrylics and/orpolybutadienes on the one hand, and aliphatic and/or aromaticisocyanates on the other, as well as precursors thereof.

[0196] 15. Polyamides and copolyamides derived from diamines,dicarboxylic acids and/or aminocarboxylic acids or the correspondinglactams, such as polyamide 4, polyamide 6, polyamide 6/6, polyamide6/10, polyamide 6/9, polyamide 6/12, polyamide 4/6, polyamide 12/12,polyamide 11 and polyamide 12; aromatic polyamides starting fromm-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without anelastomer as a modifier, for example, poly-2,4,4-trimethylhexamethyleneterephthalamide or poly-m-phenylene isophthalamide; block copolymers ofthe aforementioned polyamides with polyolefins, olefin copolymer,ionomers, chemically bonded or grafted elastomers, or polyethers such aspolyethylene glycol, polypropylene glycol or polytetramethylene glycol;and polyamides condensed during processing (RIM polyamide systems).

[0197] 16. Polyureas, polyimides, polyamide-imides, polyetherimides,polyesterimides, polyhydantoins and polybenzimidazoles.

[0198] 17. Polyesters derived from dicarboxylic acids, diols and/orhydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylcyclohexane terephthalate and polyhydroxybenzoates, aswell as block copolyether esters derived from hydroxyl-terminatedethers; PETG; PEN; PTT; and also polyesters modified with polycarbonateor MBS.

[0199] 18. Polycarbonates and polyester carbonates.

[0200] 19. Polysulfones, polyether sulfones and polyether ketones.

[0201] 20. Crosslinked polymers derived from aldehydes condensationresins such as phenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

[0202] 21. Drying and non-drying alkyd resins.

[0203] 22. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents and also halogen-containingmodifications thereof.

[0204] 23. Crosslinkable acrylic resins derived from substitutedacrylates such as epoxy acrylates, hydroxy acrylates, isocyanatoacrylates, urethane acrylates or polyester acrylates.

[0205] 24. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, isocyanates,isocyanurates, carbamates or epoxy resins.

[0206] 25. Crosslinked epoxy resins derived from aliphatic,cycloaliphatic, heterocyclic and/or aromatic glycidyl compounds such asbisphenol A and bisphenol F, which are crosslinked with hardeners suchas anhydrides or amines.

[0207] 26. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous derivatives thereof, including celluloseacetates, cellulose propionates and cellulose butyrates, or thecellulose ethers such as methyl cellulose, as well as rosins and theirderivatives.

[0208] 27. Polysiloxanes.

[0209] 28. Michael addition polymers of amines or blocked amines (e.g.,ketimines) with activated unsaturated and/or methylene compounds such asacrylates and methacrylates, maleates and acetoacetates.

[0210] 29. Mixtures or blends of any of the above, such as PP/EPDM,polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS,PC/ASA, PC/PBT, PVC/CPE, PVC/acrylate, POM/thermoplastic PUR,PC/thermoplastic polyurethane, POM/acrylate, POM/MBS, PPO/HIPS,PPO/PA6.6 and copolymers, PATENT/HDPE, PP/HDPE, PP/LDPE, LDPE/HDPE,LDPE/EVA, LDPE/EAA, PATENT/PP, PATENT/PPO, PBT/PC/ABS, PBT/PET/PC andthe like.

[0211] 30. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins includingurethane acrylates, polyether acrylates, vinyl or acryl copolymers withpendant unsaturated groups and acrylated melamines.

[0212] 31. Radiation curable compositions containing ethylenicallyunsaturated monomers or oligomers and a polyunsaturated aliphaticoligomer.

[0213] 32. Epoxymelamine resins such as light-stable epoxy resinscross-linked by an epoxy functional coetherified high solids melamineresin.

[0214] Other materials which can be stabilized include, for example:

[0215] 33. Naturally occurring and synthetic organic materials which maybe mixtures of compounds, including mineral oils, animal and vegetablefats, oils and waxes, or oils, fats or waxes based on synthetic esters(e.g., phthalates, adipates, phosphates or trimellitates) and alsomixtures of synthetic esters with mineral oils in any ratio.

[0216] 34. Aqueous emulsions of natural or synthetic rubber such asnatural latex or lattices of carboxylated styrene/butadiene copolymers.

[0217] 35. Organic dyes such as azo dyes (diazo, triazo and polyazo),anthraquinones, benzodifuranones, polycyclic aromatic carbonyl dyes,indigoid dyes, polymethines, styryl dyes, di- and triaryl carboniumdyes, phthalocyanines, quinophthalones, sulfur dyes, nitro and nitrosodyes, stilbene dyes, formazan dyes, quinacridones, carbazoles andperylene tetracarboxylic diimides.

[0218] 36. Cosmetic products, such as skin lotions, collagen creams,sunscreen, facial make-up, etc., comprising synthetic materials such asantioxidants, preservatives, lipids, solvents, surfactants, colorants,antiperspirants, skin conditioners, moisturizers etc.; as well asnatural products such as collagen, proteins, mink oil, olive oil,coconut oil, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum,aloe, etc.

[0219] 37. Cellulose-based paper formulations for use, e.g., innewsprint, cardboard, posters, packaging, labels, stationery, book andmagazine paper, bond typing paper, multi-purpose and office paper,computer paper, xerographic paper, laser and ink-jet printer paper,offset paper, currency paper, etc.

[0220] 38. Photographic film paper.

[0221] 39. Ink.

[0222] Aliphatic Polyamide

[0223] The novel alkyated para-tertiary alkyl phenyl substitutedpyrimidines and triazines of the present invention can also be used withaliphatic polyamide polymers. An “Aliphatic polyamide” is a polyamidecharacterized by the presence of recurring carbonamide groups as anintegral part of the polymer chain which are separated from one anotherby at least two aliphatic carbon atoms. Illustrative of these polyamidesare those having recurring monomeric units represented by the generalformula:

—NHC(O)RC(O)NHR¹— or —NH—R—C(O)—

[0224] or a combination hereof in which R and R¹ are the same ordifferent and are alkylene groups of at least about two carbon atoms,preferably alkylene having from about 2 to about 12 carbon atoms.Exemplary of such polyamides are polyamides formed by the reaction ofdiamines and diacids such as poly (tetramethylene adipamide)(nylon 4,6);poly(hexamethylene adipamide) (nylon 6,6); poly (hextamethyleneazelamide) (nylon 6,9); poly(hexamethylene sebacamide) (nylon 6,10);poly(heptamethylene pimelamide) (nylon 8,8); poly(nonamethyleneazelamide) (nylon 9,9); poly(decamethylene azelamide) (nylon 10,9); andthe like. Also illustrative of useful aliphatic polyamides are thoseformed by polymerization of amino acids and derivatives thereof, as forexample lactams. Illustrative of these useful polyamides arepoly(4-aminobutyric acid) (nylon 4); poly(6-aminohexanoic acid) (nylon6); poly(7-aminoheptanoic acid) (nylon 7); poly(8-aminoocatanoic acid)(nylon 8); poly(9aminononanoic acid) (nylon 9); poly(10-aminodecanoicacid) (nylon 10); poly(11-aminoundecanoic acid) (nylon 11);poly(12-aminododecanoic acid) (nylon 12); and the like. Blends of two ormore aliphatic polyamides may also be employed.

[0225] Copolymers formed from any combination of the recurring units ofthe above referenced aliphatic polyamides can be used. By way ofillustration and not limitation, such aliphatic polyamide copolymersinclude caprolactam/hexamethylene adipamide copolymer (nylon 6/6,6);hexamethylene adipamide/caprolactam copolymer (nylon 6,6/6);hexamethylene adipamide/hexamethylene-azelamide copolymer (nylon6,6/6,9); and copolymers formed from recurring units of the abovereferenced aliphatic polyamides with aliphatic/aromatic polyamiderecurring units may also be used. Examples of such copolyamides arenylon 6/6T; nylon 6,6/6, T; nylon 6/10T; nylon 6/12T; nylon 6,10/6,Tetc.

[0226] Preferred aliphatic polyamides for use in the practice of thisinvention are poly(caprolactam); poly(7-aminoheptanic acid);poly(tetramethylene adipamide); poly(hexamethylene adipamide); andmixtures thereof. The particularly preferred aliphatic polyamides arepoly(caprolatam); poly(hexamethylene adipamide); poly(tetramethyleneadipamide); and mixtures thereof.

[0227] Aliphatic polyamides useful in the practice of this invention maybe obtained from commercial sources or prepared in accordance with knownpreparatory techniques. For example, polycaprolactam may be obtainedfrom Allied Signal Inc. and poly(hexamethylene adipamide) may beobtained from DuPont Co.

[0228] The number average molecular weight of the aliphatic polyamidemay vary widely. Usually, the aliphatic polyamide is of film formingmolecular weight that is sufficiently high to form a free standing filmand sufficiently low to allow melt processing of the blend into a film.Such number average molecular weights are well known to those of skillin the film art and are usually at least about 5,000 as determined bythe formic acid viscosity method. In this method, a solution of 9.2 wt.Concentration of aliphatic polyamide in 90% formic acid at 25° C. isused. In the preferred embodiments of the invention, the number averagemolecular weight of the aliphatic polyamide is from about 5,000 to about1,000,000 and in the particularly preferred embodiments is from about10,000 to about 100,000. Amongst the particularly preferred embodiments,most preferred are those in which the molecular weight of the aliphaticpolyamide is from about 20,000 to about 40,000.

[0229] Polyurethane

[0230] Polyurethane (PUR) elastomer products (“spandex”) can bestabilized against discoloration and loss of elasticity during UV lightexposure with combinations of UV absorbers according to the inventionand hindered amine light stabilizers. Spandex fibers is a PUR elastomerproduct, which requires very specific UV absorber and hindered aminelight stabilizers properties in order to achieve optimum performance. UVabsorbers of the triazine class of this invention can be combined withpolymeric hindered amine light stabilizers (HALS) to provide outstandingperformance in achieving the desired properties for the Spandex fiberapplications.

[0231] The triazine UV absorber of the invention, used alone or incombination with HALS provides the following properties in the Spandexfiber application: (1) low color contribution at typical use levels inthe 0.5-2.0% range; (2) sufficient MW, thermal stability and lowvolatility for fiber processing and thermal exposure conditions; (3)high compatibility and permanence; (4) prevent discoloration and loss ofelasticity during exposure to UV light energy; (5) low extraction bywater and dry cleaning solvents; (6) low color development duringexposure to atmospheric pollutants, NO_(x), SO_(x), hydrocarbons, etc.;(7) low interaction with sea water and pool chemicals; (8) lowinteraction and color development with typical phenolic antioxidantsused for the thermal stabilization of Spandex fibers; and (9) lowinteraction with copper based antioxidant systems used in Nylon fibersfor Nylon/Spandex fabrics.

[0232] The triazine UV absorber with or without the polymeric HALSprovides outstanding stabilization with minimum negative effect onsecondary performance properties, such as low color development duringNO_(x) exposure and low interaction with copper based antioxidantsystems using in Nylon fibers.

[0233] As noted above, any of the triazine compounds disclosed hereincan be used to impart one or more of the properties described above toSpandex fibers when added thereto in a stabilization effective amount.

[0234] Preferably, these triazine compounds are added in combinationwith polymeric HALS. The polymeric HALS is preferablypoly[(6-morpholino-s-triazine-2,4-diyl)[2,2,6,6,-tetramethyl-4-piperidyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]]. Most preferably, thepolymeric HALS is the methylated (M) version of the above HALS, which issold by Cytec Industries, Inc. as CYASORB® UV-3529 light stabilizer.Other polymeric HALS disclosed in U.S. Pat. No. 4,331,586 are alsosuitable.

[0235] Spandex fibers are made from a polyurethane (PUR) prepolymerprepared from a diisocyanate and a glycol. There are four basicprocesses used to convert the PUR prepolymer into the fiber product.These processes are Solution Dry Spinning, Solution Wet Spinning, MeltExtrusion, and R^(e)action Spinning. The above UV stabilizer alone or incombination with HALS would be suitable for use in any or all fourprocesses.

[0236] Spandex fibers may contain a processing antioxidant system, suchas a phenolic antioxidant, or a phenolic/phosphite antioxidantcombination. In addition, pigments, such as TiO₂ are commonly used inthe fiber products.

[0237] The triazine UV absorber alone or with M-HALS can be dissolvedinto DMF or DMAC and added to the PUR prepolymer solution prior tosolution fiber spinning processes. Also, the combination can beextrusion compounded into the PUR compound used in the melt spinningprocess.

[0238] Polycarbonates

[0239] Among polymeric compounds, preference is given to thepolycarbonates, polyesters, polyamides, polyacetals, polyphenyleneoxides and polyphenylene sulfides, but especially to the polycarbonates.Those compounds are to be understood as being especially those polymersthe constitutional repeating unit of which corresponds to the formula:

[0240] wherein A is a divalent phenolic radical. Examples of A are giveninter alia in U.S. Pat. No. 4,960,863 and DE-A-3 922,496. A can bederived, for example, from hydroquinone, resorcinol,dihydroxybiphenylene or bisphenols in the broadest sense of the term,such as bis(hydroxyphenyl)alkanes, cycloalkanes, sulfides, ethers,ketones, sulfones, sulfoxides,α,α′-bis(hydroxyphenyl)-diisopropylbenzenes, for example the compounds2,2-bis(4-hydroxyphenyl)propane,2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-propane,2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,1,1-bis(4-hydroxyphenyl)cyclohexane, or from the compounds of theformulae:

[0241] In one embodiment, the preferred resins are polycarbonates basedon dihydric phenols such as 2,2-bis-(4-hydroxyphenyl)propane (bisphenolA); 2,4-bis (4-hydroxyphenyl)-2-methylbutane;1,1-bis-(4-hydroxyphenyl)-cyclohexane;2,2-bis-(3-chloro-4-hydroxyphenyl)propane; 4,4′-sulfonyldiphenol; and1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

[0242] Also preferred are polycarbonate copolymers incorporating two ormore phenols, branched polycarbonates wherein a polyfunctional aromaticcompounds is reacted with the dihydric phenol(s) and carbonateprecursor, and polymer blends of which polycarbonate comprises asignificant portion of the blend.

[0243] The most preferred resins for both layers are polycarbonatesbased on bisphenol A.

[0244] U.S. Pat. No. 5,288,788 also describes polycarbonates andpolyester carbonates, especially aromatic polycarbonates, for examplethose based on 2,2-bis(4-hydroxyphenyl)propane or1,1-bis(4-hydroxyphenyl)cyclohexane.

[0245] British Patent Appn. No. 2,290,745 describes a number of methodshave been developed to concentrate UV absorbers near or at the surfaceof polymeric materials. These include surface impregnation (see U.S.Pat. Nos. 3,309,220, 3,043,709, 4,481,664 and 4,937,026) and coating aplastic article with solutions containing thermoplastic resins and UVabsorbers (see U.S. Pat. Nos. 4,668,588 and 4,353,965). Both techniquessuffer from drawbacks including requiring additional processing steps(i.e. applying, drying or curing), and encounter difficulties associatedwith the handling of large processed articles. An additional drawback,particularly relevant to polycarbonate sheet production, is thedetrimental effect such post addition treatment would have on thesurface of the polymeric substrate.

[0246] As described in the U.S. Pat. No. 5,445,872, application ofsurface layers via coextrusion takes place in a known manner in knowncoextrusion equipment as taught in U.S. Pat. Nos. 3,487,505 and3,557,265. Coextrusion is a well recognized method of producinglaminated thermoplastic materials by simultaneously extruding variousnumbers of layers which form a single composite material. U.S. Pat. No.4,540,623 describes coextruded materials of at least forty layers. Othermethods produce as few as two or three different layers.

[0247] In one embodiment, the invention also relates to thermoplasticarticles coated with a thermoplastic layer 0.1 to 10 mil (0.00254 mm to0.254 mm), preferable 0.1 to 5 mil (0.00254 mm to 0.127 mm), thick, inwhich said layer contains 0.1% to 20% by weight of the para-tertiaryalkyl phenyl substituted pyrimidines and triazines of the presentinvention. Preferred concentrations of are 2% to 15% by weight; mostpreferred concentrations of 5% to 10% by weight.

[0248] The para-tertiary alkyl phenyl substituted pyrimidines andtriazines of the present invention may be incorporated into thethermoplastics of the surfaces layer by standard methods such as drymixing the additives with granular resin prior to extruding.

[0249] The para-tertiary alkyl phenyl substituted pyrimidine or triazinelayer may be applied to one or both sides of the thermoplastic article.

[0250] Laminated thermoplastic articles which contain additional layerssuch as a water resistant layer as found in U.S. Pat. No. 4,992,322 arealso part of the present invention.

[0251] The core layer and the coating layer may be of the samethermoplastic resin or different thermoplastic polyesters, polyestercarbonates, polyphenylene oxide, polyvinyl chloride, polypropylene,polypropylene, polyethylene, polyacrylates, polymethacrylates andcopolymers and blends such as styrene and acrylonitrile on polybutadieneand styrene with maleic anhydride.

[0252] Mixtures (polyblends) of such polymers with one another or withother polymers, for example with polyolefins, polyacrylates, polydienesor other elastomers in the form of impact strength modifiers.

[0253] The para-tertiary alkyl phenyl substituted pyrimidines andtriazines of the present invention can also be chemically bonded tosubstrates, such as polymers, thereby greatly reducing the migration ofsuch UV absorbers, e.g., out of the substrate or away from the substratesurface. The bonding mechanism of the triazines of the present inventioninvolves the formation of a bond (chemical and/or co-valent) between afunctionality attached to the amido or carbamate group, e.g., by apendant vinyl or hydroxyl group, and the “host” substrate, such as apolymer.

[0254] Incorporation of the para-tertiary alkyl phenyl substitutedpyrimidines and triazines of the invention can be brought about bycopolymerization, copolyaddition, copolycondensation, by reaction with apolymer which carries suitable functional groups, or by grafting, in amanner as disclosed in U.S. Pat. Nos. 3,423,360 and 5,189,084 which areincorporated herein by reference as if fully set forth.

[0255] Bonding of the para-tertiary alkyl phenyl substituted pyrimidinesand triazines of the invention can occur by polymerization orcopolymerization. In the case of the novel triazines of the presentinvention comprising pendant vinyl groups, polymerization orcopolymerization with at least one vinyl monomer, e.g., (meth)acrylicacid, esters of (meth)acrylic acid such as methyl acrylate, amides of(meth)acrylic acid, hydroxyethylacrylate, olefins, vinyl chloride,styrene, butadiene, isoprene and acrylonitrile can be carried out toform homopolymers or copolymers in which the vinyl group is incorporatedinto the backbone of the polymer. Polymerization or copolymerization canbe initiated by initiators, such as free radical, anionic and cationictypes, or by actinic radiation, such as UV, electron beam, x-rays andgamma irradiation from a Co⁶⁰ source, as is well known to those in thepolymerization art. Polymerization or copolymerization can be carriedout in solution, in an emulsion, in a dispersion, in the melt, or in thesolid state as is well known to those in the polymerization art.

[0256] Also, bonding of the presently claimed para-tertiary alkyl phenylsubstituted pyrimidines and triazines compounds of the present inventioncan be brought about by copolyaddition or copolycondensation. Suchincorporation can be made by addition during the synthesis of anaddition polymer or copolymer or by condensation during the synthesis ofa condensation polymer or copolymer by methods known to those skilled inthe art. For example, compounds of the formulas (I)-(V) containing theappropriate functional groups can be incorporated into polyesters,polyamides, polyurethanes, epoxy resins, melamine resins, alkyd resins,phenolic resins, polyurethanes, polycarbonates, polysiloxanes,polyacetals and polyanhydrides, to name but a few.

[0257] In addition, compounds of the formulas (I)-(V) can be bonded to amonomeric component which is then incorporated into a polymer orcopolymer, e.g., by the free radical initiated addition orcopolycondensation methods described above. Analogous methods aredisclosed in, for example, U.S. Pat. No. 5,459,222 (incorporated byreference herein for all purposes as if fully set forth) for the bondingof benzotriazole and benzophenone stabilizers to diol precursors whichare then incorporated by condensation polymerization into polyurethanesand polyesters to impart UV stabilizing properties to said polymers.

[0258] Alternately, the para-tertiary alkyl phenyl substitutedpyrimidines and triazines of the invention may also be bonded topolymers by reaction with an oligomer and/or polymer which carriessuitable functional groups. For example, at least one triazine compoundcomprising a vinyl pendant group can be added, optionally with at leastone other vinyl monomer or compound comprising a vinyl group, tounsaturated polyester resins, unsaturated polybutadiene oligomers orunsaturated rubbers and then cured by actinic radiation or by a freeradical catalyst. Or, at least one triazine compound comprising aterminal functional group, such as hydroxyl or amido, may be reactedwith a polymer and/or oligomer such as polyesters, polyurethanes andpolydiols with reactive end-groups, partially hydrolyzedpolyvinylacetate, epoxy resins, polysiloxanes and polymers comprisingmaleic anhydride, either in the main chain or as a side-chain, bymethods analogous to those well known to those of ordinary skill in theart.

[0259] Grafting is yet another way of bonding of the presently claimedpara-tertiary alkyl phenyl substituted pyrimidines and triazines topolymers and/or oligomers. Grafting may be carried out in solution, inthe melt, or in the solid state with the initiators or actinic radiationtypes discussed above for polymerization when, for example, the noveltriazines of the present invention comprising pendant vinyl groups areused. Such para-tertiary alkyl phenyl substituted pyrimidines andtriazines may be grafted to saturated polymers, e.g., polyolefins andtheir copolymers such as polyethylene, polypropylene andpoly(ethylene-vinyl acetate), or to polymers comprising unsaturatedmoieties, e.g., polybutadiene, polyisoprene, ethylene-propylene-(dienemonomer) terpolymers and polystyrene and its copolymers.

[0260] The para-tertiary alkyl phenyl substituted pyrimidines andtriazines of the present invention may be used in widely varying amountsin such applications depending upon such things as the material to bestabilized and the particular application. However, when employed as astabilizing additive for materials such as organic polymers, thepara-tertiary alkyl phenyl substituted pyrimidines and triazines of thepresent invention are typically employed in amounts from about 0.01 toabout 20% by weight, preferably from about 0.1 to about 10% by weight,and most preferably from about 0.1 to about 5% by weight, based on theweight of the material to be stabilized. In screening applications suchas sunscreening compositions, the triazines are utilized in the samerelative amounts but based on the total weight of the screening agent.

[0261] The novel stabilizers of the present invention may also beemployed in a non-bondable capacity, for example, in the stabilizationof thermoplastic polymers as set forth in the many of the previouslyincorporated references. Examples of preferred thermoplastic polymersare polyolefins and polymers comprising heteroatoms in the main chain.Preferred polymers are also thermoplastic polymers comprising nitrogen,oxygen and/or sulphur, especially nitrogen or oxygen, in the main chain.Also of interest are compositions in which the polymer is a polyolefin,for example polyethylene or polypropylene.

[0262] Incorporation into the thermoplastic polymers can be carried outby addition of the novel para-tertiary alkyl phenyl substituted triazineor pyrimidine compound and any further additives by the methodsconventional in the art. The incorporation can expediently be madebefore or during shaping, for example by mixing the pulverulentcomponents or by adding the stabilizer to the melt or solution of thepolymer, or by applying the dissolved or dispersed compounds to thepolymer, with or without subsequent evaporation of the solvent.Elastomers can also be stabilized as lattices.

[0263] The novel mixtures can also be added to the polymers to bestabilized in the form of a masterbatch which comprises these compounds,for example, in a concentration of from about 2.5 to about 25%,preferably from about 5 to about 20% by weight of the polymer.

[0264] The novel mixtures can expediently be incorporated into thepolymeric material by any number of methods, including thoseconventionally employed in the art, including by, for example: a) as anemulsion or dispersion (for example to lattices or emulsion polymers);(b) as a dry mix during mixing of additional components or polymermixtures; (c) by direct addition to the processing equipment (forexample extruders, internal mixers, etc.); or (d) as a solution or melt.

[0265] The stabilized polymer compositions obtained in this way can beconverted into shaped articles, for example fibers, films, tapes,sheets, sandwich boards, containers, pipes and other profiles, by anynumber of conventional methods, for example hot pressing, spinning,extrusion, roto-molding or injection molding. Therefore, the presentinvention additionally relates to the use of the polymer compositionaccording to the invention for the production of a shaped article.

[0266] Depending upon their ultimate end use, the para-tertiary alkylphenyl substituted pyrimidines and triazines of the present inventionmay be combined with a variety of additives conventionally employed inthe UV stabilizing art. Examples of such additives include but are notlimited to:

[0267] a. Antioxidants

[0268] (i) Alkylated monophenols such as2,6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4,6-dimethylphenol;2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol;2,6-di-tert-butyl-4-isobutylphenol; 2,6-dicyclopentyl-4-methylphenol;2-(α-methylcyclohexyl)-4,6-dimethylphenol;2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol;2,6-di-tert-butyl-4-methoxymethylphenol; nonylphenols which are liner orbranched in the side chains such as 2,6-di-nonyl-4-methylphenol;2,4-dimethyl-6-(1-methylundec-1-yl)phenol;2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol;2,4-dimethyl-6-(1-methyltridec-1-yl)phenol; and mixtures thereof.

[0269] (ii) Alkylthiomethylphenols such as2,4-dioctylthiomethyl-6-tert-butylphenol;2,4-dioctylthiomethyl-6-methylphenol;2,4-dioctylthiomethyl-6-ethylphenol; and2,6-didodecylthiomethyl-4-nonylphenol.

[0270] (iii) Hydroquinones and alkylated hydroquinones such as2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tert-butylhydroquinone;2,5-di-tert-amylhydroquinone; 2,6-diphenyl-4-octadecyloxyphenol;2,6-di-tert-butylhydroquinone; 2,5-di-tert-butyl-4-hydroxyanisole;3,5-di-tert-butyl-4-hydroxyanisole; 3,5-di-tert-butyl-4-hydroxyphenylstearate; and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

[0271] (iv) Tocopherols such as α-tocopherol, β-tocopherol,γ-tocopherol, δ-tocopherol, and mixtures thereof (vitamin E).

[0272] (v) Hydroxylated thiodiphenyl ethers such as2,2′-thiobis(6-tert-butyl-4-methylphenol); 2,2′-thiobis(4-octylphenol);4,4′-thiobis(6-tert-butyl-3-methylphenol);4,4′-thiobis(6-tert-butyl-2-methylphenol);4,4′-thiobis(3,6-di-sec-amylphenol); and4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

[0273] (vi) Alkylidenebisphenols such as2,2′-methylenebis(6-tert-butyl-4-methylphenol);2,2′-methylenebis(6-tert-butyl-4-ethylphenol);2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol];2,2′-methylenebis(4-methyl-6-cyclohexylphenol);2,2′-methylenebis(6-nonyl-4-methylphenol);2,2′-methylenebis(4,6-di-tert-butylphenol);2,2′-ethylidenebis(4,6-di-tert-butylphenol);2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol);2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol];2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol];4,4′-methylenebis(2,6-di-tert-butylphenol);4,4′-methylenebis(6-tert-butyl-2-methylphenol);1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;2,6-bis(3-tert-butyl-5-methyl-2-hydroxylbenzyl)-4-methylphenol;1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane;ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene;bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate;1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane;2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane;2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane;and 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0274] (vii) O-, - and S-benzyl compounds such as3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether;octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate;tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate;tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine;bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate;bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; andisooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0275] (viii) Hydroxybenzylate malonates such asdioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate;dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate;didodecyhnercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate;andbis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0276] (ix) Aromatic hydroxybenzyl compounds such as1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene;1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene;and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0277] (x) Triazine compounds such as2,4-bis(octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine;2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine;2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine;2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine;1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate;2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine;1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine;and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0278] (xi) Benzylphosphonates such asdimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate;diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; and thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0279] (xii) Acylaminophenols such as 4-hydroxylauranilide;4-hydroxystearanilide; and octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0280] (xiii) Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols such as methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0281] (xiv) Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- orpolyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0282] (xv) Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acidwith mono- or polyhydric alcohols such as methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)-oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0283] (xvi) Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acidwith mono- or polyhydric alcohols such as methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0284] (xvii) Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid such asN,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine;N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine;and N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

[0285] (xviii) Ascorbic acid (Vitamin C).

[0286] (xix) Aminic antioxidants such asN,N′-diisopropyl-p-phenylenediamine;N,N′-di-sec-butyl-p-phenylenediamine;N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine;N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine;N,N′-bis(1-methylheptyl)-p-phenylenediamine;N,N′-dicyclohexyl-p-phenylenediamine; N,N′-diphenyl-p-phenylenediamine;N,N′-bis(2-naphthyl)-p-phenylenediamine;N-isopropyl-N′-phenyl-p-phenylenediamine;N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine;N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine;N-cyclohexyl-N′-phenyl-p-phenylenediamine;4-(p-toluenesulfonamoyl)diphenylamine;N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine; diphenylamine;allyldiphenylamine; 4-isopropoxydiphenylamine; -phenyl-1-naphthylamine;N-(4-tert-octylphenyl)-1-naphthylamine; N-phenyl-2-naphthylamine;octylated diphenylamine such as p,p′-di-tert-octyldiphenylamine;4-n-butylaminophenol; 4-butyrylaminophenol; 4-nonanoylaminophenol;4-dodecanoylaminophenol; 4-octadecanoylaminophenol;bis(4-methoxyphenyl)amine;2,6-di-tert-butyl-4-dimethylaminomethylphenol;2,4′-diaminophenylmethane; 4,4′-diaminodiphenylmethane;N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane;1,2-bis[(2-methylphenyl)amino]ethane; 1,2-bis(phenylamino)propane;(o-tolyl)biguanide; bis[4-(1′,3′-dimethylbutyl)phenyl]amine;tert-octylated N-phenyl-1-naphthylamine; a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines; a mixture of mono- and dialkylateddodecyldiphenylamines; a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines; 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine;phenothiazine; a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines; a mixture of mono- and dialkylatedtert-octylphenothiazines; N-allylphenothiazine;N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene;N,N-bis(2,2,6,6-tetramethylpiperid-4-yl)hexamethylenediamine;bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate;2,2,6,6-tetramethylpiperidin-4-one; and2,2,6,6-tetramethylpiperidin-4-ol.

[0287] b. UV-absorbers and light stabilizers

[0288] (i) 2-(2′-Hydroxyphenyl)benzotriazoles such as2-(2′-hydroxy-5′-methylphenyl)benzotriazole;2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole;2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole;2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole;2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole;2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)-benzotriazole;2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole;2-(3′,5′-di-tert-amyl-2′-hydroxphenyl)benzotriazole;2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole; amixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole;2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]benzotriazolewith polyethylene glycol 300; and [R—CH₂CH—COO(CH₂)₃]₂ B whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl.

[0289] (ii) 2-Hydroxybenzophenones, for example the 4-hydroxy,4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivative.

[0290] (iii) Esters of substituted and unsubstituted benzoic acids suchas 4-tert-butyl-phenyl salicylate; phenyl salicylate; octylphenylsalicylate; dibenzoyl resorcinol; bis(4-tert-butylbenzoyl) resorcinol;benzoyl resorcinol; 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate; hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate; octadecyl3,5-di-tert-butyl-4-hydroxybenzoate; and2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0291] (iv) Acrylates such as ethyl α-cyano-β,β-diphenylacrylate;isooctyl α-cyano-β,β-diphenylacrylate; methyl α-carbomethoxycinnamate;methyl α-cyano-β-methyl-p-methoxycinnamate; butylα-cyano-β-methyl-p-methoxycinnamate; methylα-carbomethoxy-p-methoxycinnamate; andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

[0292] (v) Nickel compounds such as nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], including the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine; nickeldibutyldithiocarbamate; nickel salts of monoalkyl esters including themethyl or ethyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid; nickel complexes of ketoximes including 2-hydroxy-4-methylphenylundecyl ketoxime; and nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

[0293] (vi) Sterically hindered amines as well as the N derivativesthereof (e.g., N-alkyl, N-hydroxy, N-alkoxy and N-acyl), such asbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl3,5-di-tert-butyl-4-hydroxybenzylmalonate; the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid; the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine;tris(2,2,6,6-tetramethylpiperidin-4-yl)nitrilotriacetate;tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate;1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);4-benzoyl-2,2,6,6-tetramethylpiperidine;4-stearyloxy-2,2,6,6-tetramethylpiperidine;bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine; the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane; the condensate of2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane;8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione;3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;a mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine; the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; the condensate of1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]);2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;oxo-piperanzinyl-triazines or so-called PIP-T HALS, e.g., GOODRITE®3034, 3150 and 3159 and similar materials disclosed in U.S. Pat. No.5,071,981; photobondable HALS such as SANDUVOR® PR-31 and PR-32(Clariant Corp.) and similar materials disclosed in GB-A-2269819; andthe reaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decaneand epichlorohydrin. See also generally U.S. Pat. Nos. 4,619,956,5,106,891, GB-A-2269819, EP-A-0309400, EP-A-0309401, EP-A-0309402 andEP-A-0434608.

[0294] (vii) Oxamides such as 4,4′-dioctyloxyoxanilide;2,2′-diethoxyoxanilide; 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide;2,2′-didodecyloxy-5,5′-di-tert-butyloxanilide;2-ethoxy-2′-ethyloxanilide; N,N′-bis(3-dimethylaminopropyl)oxamide;2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide; and mixtures of o- andp-methoxy disubstituted oxanilides and mixtures of o- and p-ethoxydisubstituted oxanilides.

[0295] (viii) 2-(2-Hydroxyphenyl)-1,3,5-triazines disclosed in thepreviously incorporated references, such as2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine;2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-(mixediso-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine;2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine;2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine;and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

[0296] (c) Metal deactivators such as N,N′-diphenyloxamide;N-salicylal-N′-salicyloyl hydrazine; N,N′-bis(salicyloyl)hydrazine;N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine;3-salicyloylamino-1,2,4-triazole; bis(benzylidene)oxalyl dihydrazide;oxanilide; isophthaloyl dihydrazide; sebacoyl bisphenylhydrazide;N,N′-diacetyladipoyl dihydrazide; N,N′-bis(salicyloyl)oxalyldihydrazide; and N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

[0297] (d) Phosphites and phosphonites, such as triphenyl phosphite;diphenyl alkyl phosphites; phenyl dialkyl phosphites; tris(nonylphenyl)phosphite; trilauryl phosphite; trioctadecyl phosphite; distearylpentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl)phosphite;diisodecyl pentaerythritol diphosphite;bis(2,4,-di-tert-butylphenyl)pentaerythritol diphosphite;bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite;bis(isodecyloxy)pentaerythritol diphosphite;bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite;bis(2,4,6-tris(tert-butyl)phenyl)pentaerythritol diphosphite; tristearylsorbitol triphosphite;tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite;6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin;6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin;bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite; andbis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

[0298] (e) Hydroxylamines such as N,N-dibenzylhydroxylamine;N,N-diethylhydroxylamine; N,N-dioctylhydroxylamine;N,N-dilaurylhydroxylamine; N,N-ditetradecylhydroxylamine;N,N-dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine;N-hexadecyl-N-octadecylhydroxylamine;N-heptadecyl-N-octadecylhydroxylamine; and N,N-dialkylhydroxylaminederived from hydrogenated tallow fatty amines.

[0299] (f) Nitrones such as N-benzyl-alpha-phenyl nitrone;N-ethyl-alpha-methyl nitrone; N-octyl-alpha-heptyl nitrone;N-lauryl-alpha-undecyl nitrone; N-tetradecyl-alpha-tridecyl nitrone;N-hexadecyl-alpha-pentadecyl nitrone; N-octadecyl-alpha-heptadecylnitrone; N-hexadecyl-alpha-heptadecyl nitrone;N-octadecyl-alpha-pentadecyl nitrone; N-heptadecyl-alpha-heptadecylnitrone; N-octadecyl-alpha-hexadecyl nitrone; and nitrones derived fromN,N-dialkylhydroxylamines prepared from hydrogenated tallow fattyamines.

[0300] (g) Thiosynergists such as dilauryl thiodipropionate anddistearyl thiodipropionate.

[0301] (h) Peroxide scavengers such as esters of P-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters;mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole; zincdibutyldithiocarbamate; dioctadecyl disulfide; and pentaerythritoltetrakis(P-dodecylmercapto)propionate.

[0302] (i) Polyamide stabilizers such as copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

[0303] (j) Basic co-stabilizers such as melamine; polyvinylpyrrolidone;dicyandiamide; triallyl cyanurate; urea derivatives; hydrazinederivatives; amines; polyamides; polyurethanes; alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate; antimony pyrocatecholate; and tinpyrocatecholate.

[0304] (k) Nucleating agents including inorganic substances such as talcand metal oxides (e.g. titanium oxide or magnesium oxide) andphosphates, carbonates and sulfates of, preferably, alkaline earthmetals; organic compounds such as mono- or polycarboxylic acids andsalts thereof, for example 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate and sodium benzoate; and polymericcompounds such as ionic copolymers (e.g. lonomers).

[0305] (l) Fillers and reinforcing agents such as calcium carbonate;silicates; glass fibers; asbestos; talc; kaolin; mica; barium sulfate;metal oxides and hydroxides; carbon black; graphite; wood flour andflours or fibers from other natural products; and synthetic fibers.

[0306] (m) Other additives such as plasticizers, lubricants,emulsifiers, pigments, rheological additives, catalysts, levellingassistants, optical brighteners, flameproofing agents, antistatic agentsand blowing agents.

[0307] (n) Benzofuranones and indolinones such as those disclosed inU.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643,DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 and EP-A-0591102;3-[4-(2-acetoxy-ethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one;5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)-phenyl]benzofuran-2-one;3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one];5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one;3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one;3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one;and 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one.

[0308] The novel para-tertiary alkyl phenyl substituted pyrimidines andtriazines of the present invention can also be employed in multilayersystems. In such systems, a polymer composition having from about 0.1 toabout 20% by weight and preferably a relatively high content of novelstabilizer, for example, about 5-15% by weight, is applied in a thinfilm (e.g., about 5-500 μm thick and, preferably, about 10-100 μm thick)to a shaped article made from a polymer containing little or noultraviolet stabilizers. Such composition may be applied at the sametime as the shaping of the base structure, for example by coextrusion ina manner analogous to that described in U.S. Pat. No. 4,948,666(incorporated by reference herein for all purposes as if fully setforth). Alternatively, application can also be made to the ready-formedbase structure, for example by lamination with a film or by coating witha solution. The outer layer or layers of the finished article have thefunction of a UV filter, which protects the interior of the article fromUV light. The outer layer preferably contains about 0.1 to about 20%,preferably about 1 to about 15%, and most preferably about 2 to about10% by weight of the outer layer composition, of at least one of thepara-tertiary alkyl phenyl substituted pyrimidine or triazine compoundsof the present invention.

[0309] The polymers stabilized in this way are notable for highweathering resistance, especially for high resistance to UV light. Thisenables them to retain their mechanical properties, and their colorsurface properties such as gloss and distinctness of image, for a longtime even when used outside. Moreover, due to the bondable nature of thepresently claimed triazine compounds, migration of these UV absorbersbetween the layers of the multi-layer coatings can, under theappropriate circumstances, be minimized.

[0310] In another embodiment of the present invention, the novelmixtures comprising compounds of the formulas (I)-(V) can be used asstabilizers for coatings, for example for paints such as disclosed innumerous references (see, e.g., U.S. Pat. Nos. 4,619,956, 4,740,542,4,826,978, 4,962,142, 5,106,891, 5,198,498, 5,298,067, 5,322,868,5,354,794, 5,369,140, 5,420,204, 5,461,151, 5,476,937, EP-0434608 andEP-A-0444323). Of particular interest are coatings and paints for theautomobile industry. The invention therefore also relates to thosecompositions which are film-forming binders for coatings.

[0311] Such novel coating compositions comprise about 0.01 to about 20%,preferably about 0.01 to about 10%, and more preferably about 0.02 toabout 5% by weight of the binder of the coating composition of thepresently claimed para-tertiary alkyl phenyl substituted pyrimidines andtriazines of the present invention.

[0312] Multilayer systems are possible here as well (such aselectrocoat/basecoat/clearcoat systems), where the concentration of thenovel stabilizer in one or more of the layers, and typically the outerlayer such as the clearcoat, can be relatively high, for example fromabout 0.01 to about 20%, preferably about 0.01 to about 10%, and morepreferably about 0.02 to about 5% by weight of binder.

[0313] The use of the novel stabilizer in coatings is accompanied by theadditional advantage that it prevents delamination, i.e. the flaking-offof the coating from the substrate. This advantage is particularlyimportant in the case of metallic substrates, including multilayersystems on metallic substrates, and particularly epoxy e-coated metallicsubstrates.

[0314] The binder can in principle be any binder which is customary inindustry, for example those described in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp.368-426, VCH, Weinheim1991 which is incorporated herein by reference. In general, it is afilm-forming binder based on a thermoplastic or curable resin,predominantly on a curable resin. Examples of thermoplastic bindersinclude acrylics, polyesters, polyurethanes and PVC plastisols. Examplesof curable binders include functional alkyd, acrylic, polyester,phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

[0315] Such curable binders can be an ambient curable or a thermosettingbinder. Further, in some systems it may be advantageous to add a curingcatalyst to such systems. Suitable catalysts which accelerate curing ofthe binder are described, for example, in Ullmann's Encyclopedia ofIndustrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft,Weinheim 1991. Preferred binders include those which comprise afunctional acrylate resin and a crosslinking agent.

[0316] A wide variety of binders may be employed in such coatingsystems. Examples of suitable coating compositions containing specificbinders include but are not limited to:

[0317] 1. paints based on ambient curable or thermosetting alkyd,acrylate, polyester, epoxy or melamine resins or mixtures of suchresins, if desired with addition of a curing catalyst;

[0318] 2. two-component polyurethane paints based on hydroxyl-containingacrylate, polyester or polyether resins and aliphatic or aromaticisocyanates, isocyanurates or polyisocyanates;

[0319] 3. one-component polyurethane paints based on blockedisocyanates, isocyanurates or polyisocyanates which are deblocked duringbaking;

[0320] 4. two-component paints based on (poly)ketimines and aliphatic oraromatic isocyanates, isocyanurates or polyisocyanates;

[0321] 5. two-component paints based on (poly)ketimines and anunsaturated acrylate resin or a polyacetoacetate resin or amethacrylamidoglycolate methyl ester;

[0322] 6. two-component paints based on carboxyl- or amino-containingpolyacrylates and polyepoxides;

[0323] 7. two-component paints based on acrylate resins containinganhydride groups and on a polyhydroxy or polyamino component;

[0324] 8. two-component paints based on (poly)oxazolines and acrylateresins containing anhydride groups, or unsaturated acrylate resins, oraliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

[0325] 9. two-component paints based on unsaturated polyacrylates andpolymalonates;

[0326] 10. thermoplastic polyacrylate paints based on thermoplasticacrylate resins or externally crosslinking acrylate resins incombination with etherified melamine resins;

[0327] 11. paint systems based on siloxane-modified or fluorine-modifiedacrylate resins.

[0328] In addition to the binder and novel para-tertiary alkyl phenylsubstituted pyrimidines and triazines of the present invention, thecoating composition according to the invention preferably furthercomprise one or more additional ultraviolet light absorbers, includingbut not limited to those specifically listed above in section b. Theadditional UV absorbers may be, for example, anothertris-aryl-1,3,5-triazine, a 2-hydroxyphenyl-2H-benzotriazole, a2-hydroxybenzophenone, an ester of an unsubstituted benzoic acid, anacrylate, an oxamide (oxanilide), or any combination of the above.Preferably, the additional UV absorber is a2-hydroxyphenyl-2H-benzotriazole and the weight ratio of benzotriazoleto amido or carbamate triazine is 4:1 to 1:4. More preferably, theweight ratio of benzotriazole to amido or carbamate triazine is 2:1 to1:2.

[0329] To achieve maximum light stability, it is of particular interestto add sterically hindered amines, examples of which are set out in theabove-mentioned section b(vi). The invention therefore also relates to acoating composition which, in addition to the binder, the novelpara-tertiary alkyl phenyl substituted pyrimidines and triazines and,optionally, additional UV absorbers, comprises a light stabilizer of thesterically hindered amine type. The sterically hindered amine isemployed in an amount of about 0.01 to 5% by weight based on the weightof the solid binder, preferably about 0.02 to 2% by weight.

[0330] One specific example of such a sterically hindered amine is a2,2,6,6-tetramethyl piperazinone containing at least one group of theformula:

[0331] in which J is, for example, hydrogen, hydroxyl, alkyl (such asmethyl), alkoxy (such as methoxy) or acyl.

[0332] More preferably the stabilizer is a 2,2,6,6-tetraalkylpiperidinederivative containing at least one group of the formula:

[0333] in which J is, for example, hydrogen, hydroxyl, alkyl (such asmethyl), alkoxy (such as methoxy) or acyl.

[0334] Examples of tetraalkylpiperidine derivatives which can be used incombination with the present trisaryl-1,3,5-triazine compounds are givenin U.S. Pat. Nos. 4,314,933, 4,344,876, 4,426,471, 4,426,472, 4,619,956,5,004,770, 5,006,577, 5,064,883, 5,112,890, 5,124,378, 5,106,891,5,204,473, and 5,461,15 1, which are incorporated by reference hereinfor all purposes as if fully set forth. It is particularly expedient toemploy the following tetraalkylpiperidine derivatives, as well as theirN-alkyl, N-acyl, N-hydroxyl and N-alkoxy analogs (where not alreadyincluded in the following list): bis(2,2,6,6-tetramethylpiperid-4-yl)succinate, bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperid-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperid-4-yl)butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate,tetra(2,2,6,6-tetramethylpiperid-4-yl)butane-1,2,3,4-tetracarboxylate,tetra(1,2,2,6,6-pentamethylpiperid-4-yl)butane-1,2,3,4-tetracarboxylate,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane,and8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione.Commercially available examples of these and other tetraalkylpipieridinederivatives include SANDLVOR® 3050, 3052, 3055, 3056, 3058, PR-31 andPR-32 (Clariant Corp.); TINUVIN® 079L, 123, 144, 292, 440L and 622LD(Ciba Specialty Chemicals); CHIMASORB® 119 and 944 (Ciba SpecialtyChemicals); and CYASORB® UV-3346, UV 3529, UV-3853, UV-500 and UV-516(Cytec Industries Inc.).

[0335] Apart from the binder, the para-tertiary alkyl phenyl substitutedpyrimidine or triazine, and, if used, the additional ultraviolet lightabsorber or stabilizer, the coating composition can also comprisefurther components, examples being solvents, pigments, dyes,plasticizers, stabilizers, thixotropic agents, drying catalysts and/orleveling agents. Examples of possible components are those described inmany of the previously incorporated references as well as Ullmann'sEncyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp.429-471, VCH, Weinheim 1991; and Calbo, Leonard J., ed., Handbook ofCoatings Additives, New York:Marcel Dekker (1987).

[0336] Possible drying catalysts or curing catalysts are, for example,organometallic compounds, amines, acids, amino-containing resins and/orphosphines.

[0337] Examples of acid catalysts are mineral acids, aliphatic andaromatic sulfonic acids (e.g. p-toluene sulfonic acid,dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid),oxalic acid, maleic acid, hexamic acid, phosphoric acid, alkyl phosphateesters, phthalic acid and acrylic acid copolymers.

[0338] Examples of organometallic compounds are metal carboxylates,especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metalchelates, especially those of the metal Al, It or Zr, or organometalliccompounds such as organotin compounds, for example. Examples of metalcarboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Znor Cu, the naphthenates of Mn and Co or the corresponding linoleates,resinates or tallates. Examples of metal chelates are the aluminum,titanium or zirconium chelates of acetylacetone, ethyl acetylacetate,salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyltrifluoroacetylacetate and the alkoxides of these metals. Examples oforganotin compounds are dibutyltin oxide, dibutyltin dilaurate ordibutyltin dioctoate.

[0339] Examples of amine drying or curing catalysts are, in particular,tertiary amines, for example tributylamine, triethanolamine,N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine,N-methylmorpholine or diazabicyclooctane (triethylenediamine) and saltsthereof. Further examples are quaternary ammonium salts, for exampletrimethylbenzylammonium chloride. Amino-containing resins aresimultaneously binder and curing catalyst. Examples thereof areamino-containing acrylate copolymers.

[0340] The curing catalyst used can also be a phosphine, for exampletriphenylphosphine.

[0341] Another type of curing catalyst is a peroxide which can be used,for example, to cure a gel coating for a fiberglass article.

[0342] The novel coating compositions can also be radiation-curablecoating compositions. In this case, the binder essentially comprisesmonomeric or oligomeric compounds containing ethylenically unsaturatedbonds, which after application are cured by actinic radiation, i.e.converted into a crosslinked, high molecular weight form. Where thesystem is UV-curing, it generally contains a photoinitiator as well.Corresponding systems are described in the above-mentioned publicationUllmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18,pages 451-453. In radiation-curable coating compositions, the novelstabilizers can also be employed without the addition of stericallyhindered amines.

[0343] The novel coating compositions according to the invention can beapplied to any desired substrates, for example to metal, wood, plastic,fiberglass or ceramic materials. The coating compositions can bepigmented mono-coats or multi-layer (primer/basecoat/clearcoat) systemstypical of automotive finishes. In the latter case, the novel coatingcomposition can be used for either the base coat, or clear coat, or forboth layers. If the topcoat of an automotive finish comprises twolayers, of which the lower layer is pigmented and the upper layer is notpigmented, the novel coating composition can be used for either theupper or the lower layer or for both layers, but preferably for theupper topcoat layer.

[0344] The novel coating compositions can be applied to the substratesby the customary methods, for example by brushing, spraying, pouring,dipping or electrophoresis; see also Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp. 491-500.

[0345] Depending on the binder system, the coatings can be cured at roomtemperature or by heating. Thermosetting coatings are preferably curedat 50-150° C. and, in the case of powder coatings, even at highertemperatures.

[0346] The coatings obtained in accordance with the invention haveexcellent resistance to the damaging effects of light, oxygen and heat;particular mention should be made of the good light stability andweathering resistance of the coatings thus obtained, for example paints.

[0347] The invention therefore also relates to a coating, in particulara paint, which has been stabilized against the damaging effects oflight, oxygen and heat by a content of the compound of the formulas(I)-(V), according to the invention. The paint can be a pigmentedmono-coat which comprises a film-forming binder and an organic pigmentor dye, an inorganic pigment, a metallic pigment, or a mixture thereof.The paint may also be a composition which comprises a primer in adhesionto a metal or plastic substrate; a pigmented basecoat that is inadhesion to the primer and which comprises a film-forming binder and anorganic pigment or dye, an inorganic pigment, a metallic pigment, or amixture thereof; and a clear coat that is in adhesion to the base coatand which comprises a film-forming binder and optionally a transparentpigment. One especially preferred use is a paint which is a cleartopcoat for automobile original equipment manufacture (OEM) and/orrefinish applications.

[0348] The invention furthermore relates to a process for stabilizing acoating based on polymers against damage by light, oxygen and/or heat,which comprises mixing with the coating composition a mixture comprisinga compound of a para-tertiary alkyl phenyl substituted pyrimidine ortriazine and to the use of mixtures comprising para-tertiary alkylphenyl substituted pyrimidine or triazine compound in coatingcompositions as stabilizers against damage by light, oxygen and/or heat.

[0349] The coating compositions can comprise an organic solvent orsolvent mixture in which the binder is soluble. The coating compositioncan otherwise be an aqueous solution or dispersion. The vehicle can alsobe a mixture of organic solvent and water. The coating composition maybea high-solids paint or can be solvent-free (e.g. a powder coatingmaterial).

[0350] The pigments can be inorganic, organic or metallic pigments. Thenovel coating compositions preferably contain no pigments and are usedas a clearcoat.

[0351] Likewise preferred is the use of the coating composition as atopcoat for applications in the automobile industry, especially as apigmented or unpigmented topcoat of the paint finish. Its use forunderlying coats, however, is also possible.

[0352] The para-tertiary alkyl phenyl substituted pyrimidine ortriazines of this invention may be applied topically by polishing asurface with a composition comprising the para-tertiary alkyl phenylsubstituted pyrimidine or triazines and an inert carrier such assolvent, petroleum jelly, silicone oil in water emulsions, or automotivepaint wax, e.g. Carnauba wax. These topical treatment compositions maybe used to stabilize coating films, fabrics, leather, vinyl and otherplastics and wood.

[0353] Preference is also given to the use of the novel para-tertiaryalkyl phenyl substituted pyrimidine or triazine compounds inphotographic materials as stabilizer against damage by light, especiallyby UV light. The invention therefore also relates to a photographicmaterial comprising an para-tertiary alkyl phenyl substituted pyrimidineor triazine compound.

[0354] The compounds according to the invention can be used forphotosensitive materials of all kinds. For example, they can be employedfor color paper, color reversal paper, direct-positive color material,color negative film, color positive film, color reversal film and othermaterials. They are preferably used, inter alia, for photosensitivecolor material which comprises a reversal substrate or which formspositives.

[0355] Furthermore, the novel compounds can be combined with other UVabsorbers, especially those which are dispersible in aqueous gelatin,for example with hydroxyphenylbenzotriazoles (cf. for example U.S. Pat.Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701), benzophenones,oxanilides, cyanoacrylates, salicylates, or acrylonitriles orthiazolines. In this context it is advantageous to employ these further,oil-dissolved UV absorbers in the photographic material in layers otherthan those comprising the novel UV absorbers.

[0356] The present invention also encompasses compositions containingone or more binders. In particular, the binder may comprise an alkyd,acrylic, polyester, phenolic, melamine, epoxy or polyurethane resin, orblends thereof. Examples of such binders include, but are not limitedto:

[0357] (a) cold- or hot-crosslinkable alkyd, acrylate, polyester, epoxyor melamine resins or mixtures of such resins;

[0358] (b) a two-component polyurethane system comprisinghydroxyl-containing acrylate, polyester or polyether resins andaliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

[0359] (c) a one-component polyurethane system comprising blockedisocyanates, isocyanurates or polyisocyanates which are deblocked duringbaking;

[0360] (d) a two-component system comprising (poly)ketimines andaliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

[0361] (e) a two-component system comprising (poly)ketimines and anunsaturated acrylate resin or a polyacetoacetate resin or amethacrylamidoglycolate methyl ester;

[0362] (f) a two-component system comprising carboxyl- oramino-containing polyacrylates and polyepoxides;

[0363] (g) a two-component system comprising acrylate resins containinganhydride groups and on a polyhydroxy or polyamino component;

[0364] (h) a two-component system comprising (poly)oxazolines andacrylate resins containing anhydride groups, or unsaturated acrylateresins, or aliphatic or aromatic isocyanates, isocyanurates orpolyisocyanates;

[0365] (i) a two-component system comprising unsaturated polyacrylatesand polymalonates;

[0366] (j) a thermoplastic polyacrylate system comprising thermoplasticacrylate resins or externally crosslinking acrylate resins incombination with etherified melamine resins; and

[0367] (k) a system comprising siloxane-modified or fluorine-modifiedacrylate resins.

[0368] Such binder-containing compositions may further comprise a curingcatalyst, or an organic solvent, and may be radiation-curable. Inparticular, such compositions may serve as coating compositions.

[0369] In particular, it is possible successfully to stabilizephotographic materials similar to those described in U.S. Pat. No.4,518,686.

[0370] The invention therefore additionally relates to a photographicmaterial comprising, on support, a blue-sensitive, a green-sensitiveand/or a red-sensitive silver-halide emulsion layer and, if desired, aprotective layer, with a layer comprising a UV absorber being arrangedabove the uppermost silver-halide emulsion layer, wherein the UVabsorber is a para-tertiary alkyl phenyl substituted pyrimidine ortriazine compound.

[0371] Preference is additionally given to photographic materials whichhave a layer comprising a compound of the formula (I)-(V) above theuppermost silver-halide emulsion layer and/or between the green- andred-sensitive silver-halide emulsion layers.

[0372] Furthermore, it may be advantageous for all or some of the saidlayers which can comprise a UV absorber to have a UV absorber mixtureand/or a further UV absorber which is dispersible in aqueous gelatin,but a compound of the formula (I)-(V) must be present at least in onelayer.

[0373] The novel material preferably has gelatin interlayers between thesilver-halide emulsion layers.

[0374] Preference is given to photographic materials in which the silverhalide in the blue-sensitive, green-sensitive and/or red-sensitive layeris silver chloride bromide comprising at least 90 mol % of silverchloride.

[0375] The compounds of the formula (I)-(V), which are used inaccordance with the invention, can be incorporated, alone or togetherwith the color coupler and, if used, further additives, into the colorphotographic materials by dissolving the compounds beforehand inhigh-boiling organic solvents. It is preferred to use solvents whichboil at higher than 160° C. Typical examples of such solvents are theesters of phthalic acid, phosphoric acid, citric acid, benzoic acid orof fatty acids, or alkylamides and phenols.

[0376] Preferred color couplers for use in the compositions of theinvention, examples of such compounds, further additives such as colorcast inhibitors, DIR couplers and further light stabilizers, such as UVabsorbers, phenols, phosphorus (III) compounds, organometalliccomplexes, hydroquinones and hydroquinone ethers, and more precisedetails on the structure of various photographic materials, can befound, for example, in the publications EP-A-0531258 and EP-A-0520938and in the literature cited therein.

[0377] The invention also relates to a process for the stabilization ofpolyolefin or polyolefin copolymer films for agricultural applications,especially greenhouse applications, this polyolefin or polyolefincopolymer film having improved light stability and pesticide resistance,comprising incorporation of a sterically hindered amine and a metaloxide of hydroxide selected from oxides of zinc, aluminum, calcium andmagnesium, and hydroxides of zinc, aluminum and calcium, into thepolyolefin or polyolefin copolymer. A further subject of the inventionis a greenhouse, characterized in that it is covered by a polyolefin orpolyolefin copolymer film having improved light stability and pesticideresistance and stabilized with a sterically hindered amine and a metaloxide or hydroxide selected from oxides of zinc, aluminum, calcium andmagnesium, and hydroxides of zinc, aluminum and calcium, and a processfor stabilizing a polyolefin or polyolefin copolymer greenhouse filmagainst detrimental effects of pesticides and light, oxygen and/or heat,which process comprises incorporation of a sterically hindered amine anda metal oxide or hydroxide selected from oxides of zinc, aluminum,calcium and magnesium, and hydroxides of zinc, aluminum and calcium,into said greenhouse film.

[0378] Further subjects of the invention are the use of a polyolefincopolymer film stabilized with a sterically hindered amine and a metaloxide or hydroxide selected from oxides of zinc, aluminum, calcium andmagnesium, and hydroxides of zinc, aluminum and calcium for agriculturalapplications involving pesticides, especially greenhouse applications,and the use of a sterically hindered amine in combination with a metaloxide or hydroxide selected from oxides of zinc, aluminum, calcium andmagnesium, and hydroxides of zinc, aluminum, calcium and magnesium, andhydroxides of zinc, aluminum and calcium for the stabilization ofpolyolefin or polyolefin copolymer films in contact with pesticidesagainst photodegradation and damage by pesticides.

[0379] To form a film, forcing a quantity of the said melted compositionthrough a film die, such as a flat film die or a circular blown filmdie, and forming a film therefrom. In the case where the composition isused to form a film therefrom, it is contemplated that the films may beunoriented, or may be subjected to a conventional operation to impart adegree of orientation on the film. Such a film may be oriented in onedirection, such as in the machine direction, such as in the “machinedirection” and/or the “transverse direction”, or may be oriented in bothdirections, or “biaxially” oriented.

[0380] The present invention is also suitable for sheet applications.

[0381] The para-tertiary alkyl phenyl substituted pyrimidine or triazinecompounds of the formula (I)-(V) are suitable for the photochemicalstabilization of undyed, dyed or printed fiber materials comprising forexample, silk, leather, wool, polyamide or polyurethanes and especiallycellulose-containing fiber materials of all kinds. Examples of suchfiber materials are the natural cellulose fibers, such as cotton, linen,jute and hemp and also viscose staple fiber and regenerated cellulose.Preferred textile fiber materials are those of cotton. The triazine andpyrimidine compounds of the present invention are also suitable for thephotochemical stabilization of hydroxyl-containing fibers in blendfabrics, for example blends of cotton with polyester fibers or polyamidefibers. A further preferred area of application relates to the blockingor reduction of the UV radiation which passes through theabove-mentioned textile materials (LTV cutting) and the heightened sunprotection which textile materials finished with a novel compound offerto the human skin.

[0382] To this end, one or a number of different compounds of theformula (I)-(V) are applied to the textile fiber material by one of thecustomary dyeing methods, advantageously in a quantity of 0.01 to 5% byweight, preferably 0.1 to 3% by weight and, in particular, from 0.25 to2% by weight, based on the weight of the fiber material.

[0383] The para-tertiary alkyl phenyl substituted pyrimidine or triazinecompounds can be applied to the fiber material in various ways and fixedon the fiber, especially in the form of aqueous dispersions or printingpastes.

[0384] The textile fiber materials finished with the novel compounds ofthe formula (I)-(V) possess improved protection against photochemicalbreakdown of the fiber and yellowing phenomena and, in the case of dyedfibre material, are of enhanced (hot) light fastness. Particularemphasis should be drawn to the greatly improved photoprotective effectof the treated textile fiber material and, in particular, the goodprotective effect with respect to short-wave UV-B rays. This ismanifested by the fact that the textile fiber material finished with anpara-tertiary alkyl phenyl substituted pyrimidine or triazine compoundhas, relative to untreated fabric, a greatly increased sun protectionfactor (SPF).

[0385] The sun protection factor is defined as the quotient of the doseof UV radiation which damages protected skin to that which damagesunprotected skin. Accordingly, a sun protection factor is also a measureof the extent to which untreated fiber materials and fiber materialstreated with a novel compound of the formulas (I)-(V) are permeable toUV radiation. The determination of the sun protection factor of textilefiber materials is explained, for example, in WO94/04515 or in J. Soc.Cosmet. Chem. 40, 127-133 (1989) and can be carried out analogouslythereto.

[0386] Yet another use of the UV absorbers according to the invention isin the stabilization of intra-ocular and contact lenses.

[0387] The inventive UV absorbers are suitable as photoprotective agentsin cosmetic preparations. The invention additionally relates, therefore,to a cosmetic preparation comprising at least one para-tertiary alkylphenyl substituted pyrimidine or triazine compound and cosmeticallyacceptable carriers or auxiliaries.

[0388] The novel cosmetic composition contains from 0.1 to 15% byweight, preferably from 0.5 to 10% by weight, based on the overallweight of the composition, of a para-tertiary alkyl phenyl substitutedpyrimidine or triazine UV absorber and a cosmetically acceptableauxiliary.

[0389] The cosmetic composition can be prepared by physically mixing thenovel UV absorber with the auxiliary by means of customary methods, forexample by simply stirring together the two materials.

[0390] The cosmetic preparation according to the invention can beformulated as a water-in-oil or oil-in-water emulsion, as an oil-in-oilalcohol lotion, as a vesicular dispersion of an ionic or nonionicamphiphilic lipid, as a gel, solid stick or as an aerosol formulation.

[0391] As a water-in-oil or oil-in-water emulsion, the cosmeticallyacceptable auxiliary preferably contains from 5 to 50% of an oily phase,from 5 to 20% of an emulsifier and from 30 to 90% water. The oil phasecan comprise any oil which is suitable for cosmetic formulations, e.g.,one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, afatty acid ester or a fatty alcohol. Preferred mono- or polyols areethanol, isopropanol, propylene glycol, hexylene glycol, glycerol andsorbitol.

[0392] For these cosmetic formulations, it is possible to use anyconventionally employed emulsifier, e.g., one or more ethoxylated estersof naturally occurring derivatives, i.e., polyethoxylated esters ofhydrogenated castor oil; or a silicone oil emulsifier such as siliconepolyol; an unmodified or ethoxylated fatty acid soap; an ethoxylatedfatty alcohol; an unmodified or ethoxylated sorbitan ester; anethoxylated fatty acid; or an ethoxylated glyceride.

[0393] The cosmetic formulation can also comprise further components,for example emollients, emulsion stabilizers, skin moisteners, tanningaccelerators, thickeners such as xanthan, moisture retention agents suchas glycerol, preservatives, or fragrances and colorants.

[0394] The novel cosmetic formulations are notable for good protectionof human skin against the damaging effect of sunlight while at the sametime providing for reliable tanning of the skin.

[0395] The invention will now be illustrated by the following examples.The examples are not intended to be limiting of the scope of the presentinvention. In conjunction with the general and detailed descriptionsabove, the examples provide further understanding of the presentinvention.

EXAMPLES

[0396] Examples and reaction schemes for producing specific examples ofpara tertiary alkyl phenyl substituted triazines in accordance with theinvention are provided below. While the following examples illustratepreparations with one or more para tertiary alkylated phenyl compounds,one of ordinary skill will understand that these reactions may also becarried out with any of a variety of other tertiary alkylated phenylcompounds, where when necessary, reactive substituents on such othertertiary alkylated phenyl compounds are protected in accordance withprocedures and reagents well known and understood by those of ordinaryskill.

Preparative Examples Example 1

[0397] Preparation of2,4-bis(4-tert-butylphenyl)-6-chloro-1,3,5-triazine

[0398] To a 2-neck flask equipped with a reflux condenser, an argoninlet, a magnetic stirring bar and a glass stopper was introduced 9.2 gof cyanuric chloride. To it was added 125 mL of tert-butylbenzenefollowed by 8 g of aluminum chloride at room temperature. The reactionmixture was then gradually heated to 65° C. and kept at this temperaturefor 3.5 hr. At this stage an additional 8 g of aluminum trichloride wasadded and the reaction mixture was heated at 75° C. for 3 hr. Theheating was discontinued and the reaction mixture was left at roomtemperature overnight and then treated with 300 mL of ice-cold diluteHCl for 2 hr. The mixture was extracted with methylene chloride and theorganic layer separated, washed with water, dried over anhydrous sodiumsulfate and concentrated under reduced pressure to dryness. The residueso obtained was treated with acetone. The precipitated material wasfiltered off which was characterized to be mainly2,4,6-tris(4-tert-butylphenyl)-1,3,5-triazine. The filtrate wasconcentrated and purified by column chromatography to give 4.6 g of acompound characterized to be2,4-bis(4-tert-butylphenyl)-6-chloro-1,3,5-triazine.

Example 2

[0399] Preparation of2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxyphenyl)-1,3,5-triazine(Compound B)

[0400] To a 2-neck flask equipped with a reflux condenser, an argoninlet, a magnetic stirring bar and a glass stopper was introduced 3.79 gof 2,4-bis(4-tert-butylphenyl)-6-chloro-1,3,5-triazine of example 1. Toit was added 30 mL of chlorobenzene, 1.21 g of resorcinol and 2 g ofaluminum chloride at room temperature. The reaction mixture was heatedat 85° C. for 6 hr. The heating was discontinued and the reaction wasallowed to cool to room temperature. To it was then added 5% ice-coldaq. HCl, and the mixture concentrated under reduced pressure. Theresidue was washed with water and dried to give 4.4 g of a productcharacterized to be2,4-bis(4-tert-butylphenyl)-6-(2,4-dibydroxyphenyl)-1,3,5-triazine.

Example 2

[0401] Aternative Procedure

[0402] To a stirred suspension of 30 g of cyanuric chloride in 180 mL ofo-dichlorobenzene (ODCB) under nitrogen was added 65.1 g of anhydrousaluminum chloride. Concentrated hydrochloric acid (3.9 g) was added over35 min., maintaining the temperature below 24° C. Thereafter, themixture was stirred for 2 hr at room temperature. The mixture was cooledto 1° C. and 54.5 g of tert-butylbenzene was added over 2.5 hr, whilemaintaining the temperature at between about 1° C. to about 4° C. Themixture was then slowly allowed to warm to room temperature and stirredfor 20.5 hr. HPLC analysis detected 83% conversion of cyanuric chloride.

[0403] The reaction mixture was heated to 65° C. and 18 g of resorcinolwas added over 35 min. The mixture was then heated for 2.5 hr at betweenabout 75° C. to about 95° C. The mixture was cooled and 75 mL of methylisobutyl ketone (MIBK) and 300 mL of 5% aqueous hydrochloric acid wereadded. The MIBK and ODCB were removed by azeotropic distillation. Duringthis time, the product precipitated. After cooling to room temperature,the aqueous layer was decanted from the solids, the former beingtriturated with water. The solids were collected by filtration, washedwith water, air-dried, and then dried in vacuo.

[0404] The dried solid was extracted with methylene chloride andfiltered. The filtrate was concentrated under reduced pressure andpurified by column chromatography using silica gel and methyl chlorideas the eluant. The product crystallized from the eluant to give a yellowsolid identified as2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxypheynyl)-1,3,5-triazine byHPLC and HPLC/MS.

Example 3

[0405] Preparation of2,4-bis(4-tert-butylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine(Compound C)

[0406] To a 2-neck flask equipped with a reflux condenser, an argoninlet, a magnetic stirring bar and a glass stopper was introduced 2.25 gof 2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxyphenyl)-1,3,5-triazine ofexample 2. To it was added 30 mL of acetone, 3.45 g of anhydrouspotassium carbonate and 0.9 mL of 1-iodooctane. The contents were heatedto reflux for 6 hr. The reaction mixture was cooled to room temperature,diluted with methylene chloride and filtered through Celite. Thefiltrate was concentrated under reduced pressure to give 3.7 g of aresidue which was purified by column chromatography over silica gel togive 2.26 g of a pure product characterized to be2,4-bis(4-tert-butylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazinebased on NMR and mass spectra.

Example 4

[0407] Preparation of2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxy-5-hexylphenyl)-1,3,5-triazine(Compound D)

[0408] To a stirred suspension of 30 g of cyanuric chloride in 180 mL ofo-dichlorobenzene (ODCB) under nitrogen was added slowly 65.1 g ofaluminum chloride. Concentrated hydrochloric acid (3.9 g) was added over20 min, maintaining the temperature below 26° C. The reaction mixturewas then stirred at room temperature for 2 hr. The mixture was cooled to0° C. and 54.5 g of tert-butylbenzene was added over 2 hr. The reactionmixture was allowed to warm to room temperature and stirred for 40 hr.HPLC analysis showed complete consumption of cyanuric chloride.

[0409] The reaction mixture was heated to 80° C. and 34.7 g of4-hexylresorcinol was added slowly. After stirring at 80° C. for 3 hr,the reaction mixture was quenched with water and extracted withmethylene chloride. The combined methylene chloride extracts wereconcentrated under reduced pressure. The residue was crystallized fromhexane and dried in vacuo to give 31 g of2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxy-5-hexylphenyl)-1,35-triazine in >96% purity by HPLC (area % at 290 nm).

Example 5

[0410] Preparation of2,4-bis(4-tert-butylphenyl)-6-(2-hydroxy-4-octyloxy-5-hexylphenyl)-1,3,5-triazine(Compound E)

[0411] A stirred mixture of2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxy-5-hexylphenyl)-1,3,5-triazine,5 g of 1-iodooctane, 1 g of Aliquat® 336 (tricaprylmethylammoniumchloride), 14 g anhydrous potassium carbonate, and 200 mL methylisobutyl ketone (MIBK) was heated at 115-120° C. for 5 hr, and thenallowed to cool to room temperature. The mixture was extracted withmethylene chloride and the combined methylene chloride extracts wereconcentrated under reduced pressure. The resulting semi-solid residuewas recrystallized from acetone to give 12 g of2,4-bis(4-tert-butylphenyl)-6-(2-hydroxy-4-octyloxy-5-hexylphenyl)-1,3,5-triazineas a yellow solid in 97% purity as determined by HPLC (area % at 290nm). A second recrystallization from acetone yielded an analyticalsample (100% purity by HPLC).

Example 6

[0412] Preparation of2,4-bis(4-tert-butylphenyl)-6-(2-acetoxy-4-octyloxyphenyl)-1,3,5-triazine(Compound F)

[0413] To a 2-neck flask equipped with a reflux condenser, an argoninlet, a magnetic stirring bar and a glass stopper was introduced 1.4 gof2,4-bis(4-tert-butylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazineof example 3. To it was added 5 mL of pyridine, 1.0 mL of pyridine and25 mg of 4-dimethylaminopyridine. The contents were heated at 115° C.for 3 hr. The reaction mixture was cooled to room temperature and pouredinto ice-cold water and stirred for 1 hr. The precipitaed material wasfiltered and dissolved in methylene chloride. The solution thus obtainedwas first washed with dilute HCl and then with water, dried overanhydrous sodium sulfate and concentrated under reduced pressure. Theresidue so obtained was crystallized with hexane to give 1.06 g of apure compound characterized to be2,4-bis(4-tert-butylphenyl)-6-(2-acetoxy-4-octyloxyphenyl)-1,3,5-triazinebased on NMR and mass spectra.

Example 7

[0414] Preparation of2,4-bis-(4-tert-butylphenyl)-6-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-1,3,5-triazine(Compound G)

[0415] To a stirred mixture of 14 g of2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxyphenyl)-1,3,5-triazine, 10.8g of anhydrous potassium carbonate, 0.47 g of potassium iodide, and 90mL of acetone was added 3.7 mL (4,2 g) of ethyl chloroacetate. Themixture was stirred at reflux for 3 hr, and then cooled to roomtemperature. The solids were removed by filtration and washed withmethylene chloride. The product was crystallized from the combinedfiltrate, washed with cold acetone, and dried in vacuo to give 12.5 g of2,4-bis(4-tert-butylphenyl)-6-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-1,3,5-triazineas a near white powder. The structure was verified by ¹H-NMRspectroscopy.

Example 8

[0416] Preparation of2-(2-hydroxy-4-ethoxycarbonylmethoxy-5-hexylphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine(Compound H)

[0417] To a stirred mixture of 10 g of2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxy-5-hexylphenyl)-1,3,5-triazine,7.4 g of anhydrous potassium carbonate, 0.5 g of potassium iodide, and80 mL of acetone was added 2.2 mL (2.5 g) of ethyl chloroacetate. Themixture was stirred at reflux for 2.5 h and then allowed to cool to roomtemperature. The solids were removed by filtration and washed withmethylene chloride. The combined filtrates were concentrated underreduced pressure to a volume of 75 mL and diluted with 50 mL ofmethanol. The resulting solid was collected by filtration and washedwith methanol. After drying in vacuo, 10 g of2,6-bis(4-tert-butylphenyl)-6-(2-hydroxy-4-ethoxycarbonylmethoxy-5-hexylphenyl)-1,3,5-triazinewas obtained. The structure was verified by ¹HNMR spectroscopy.

Example 9

[0418] Preparation of2,4-bis(4-tert-butylphenyl)-6-[2-hydroxy-4-(N-(n-butyl)-N-(2-hydroxyethyl)methanamidooxy)phenyl]-1,3,5-triazine(Compound I)

[0419] A mixture of 6 g of2,4-bis(4-tert-butylphenyl)-6-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-1,3,5-triazine,4 g of butyl ethanolamine, 0.13 g of

[0420] 4-demethylaminopyridine, and 30 mL xylenes was stirred at reflux.After 8 hr, HPLC analysis (are % at 290 nm) showed complete conversionof starting material to one product. The mixture was allowed to cool andwas concentrated under reduced pressure. The residue was crystallizedfrom 100 mL of hexanes. The product was collected by filtration, washedwith ice-cold hexanes, and dried in vacuo to give 7 g of2,4-bis(4-tert-butylphenyl)-6-[2-hydroxy-4-(N-(n-butyl)-N-(2-hydroxyethyl)methanamidooxy)phenyl]-1,3,5-triazineas a pale yellow solid (>90% purity by HPLC). The structure was verifiedby ¹HNMR spectroscopy.

Example 10

[0421] Preparation of2,4-bis(4-tert-butylphenyl)-6-[2-hydroxy-4-(N-(n-butyl)-N-(2-hydroxyethyl)methanamidooxy-5-hexylpheynyl]-1,3,5-triazine(Compound J)

[0422] A mixture of 5 g of 2,4-bis(4-tert-butylphenyl)-6-(2

[0423] -hydroxy-4-ethoxycarbonylmethoxy-5-hexylphenyl)-1,3,5-triazine, 4g of butyl ethanolamine, 0.12 g of 1 4-dimethylaminopyridine, and 30 mLof xylenes was stirred at reflux. After 12 hr, HPLC analysis showedcomplete conversion of starting material to one product. The mixture wasallowed to cool and was concentrated under reduced pressure. The residuewas crystallized from 150 mL of hexanes. The product was collected byfiltration, washed with ice-cold hexanes, and dried in vacuo to give2,4-bis(4-tert-butylphenyl)-6-[2-hydroxy-4-(N-(n-butyl)-N-(2-hydroxyethyl)methanamidooxy)phenyl]-1,3,5-triazineas a pale yellow solid. The structure was verified by ¹HNMRspectroscopy.

Example 12

[0424] Preparation of2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxyphenyl)-1,3,5-triazine,4-O-benzenesulfonate ester (Compound K)

[0425] A stirred mixture of 12 g of2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxyphenyl)-1,3,5-triazine, 13.8g of anhydrous potassium carbonate and 100 mL of tetrahydrofuran undernitrogen was cooled to 4° C. A solution of 4.1 mL (5.7 g) ofbenzenesulfonyl chloride in 20 mL of THF was added over 20 min. Theresulting mixture was stirred at reflux for 32 hr. HPLC analysis showedcomplete conversion of starting material. The mixture was allowed tocool to room temperature and 10 mL of methanol was added. The mixturewas filtered and concentrated under reduced pressure. The residue wastriturated with 200 mL of hexanes and filtered, triturated with 250 mLof refluxing methanol, filtered hot, and washed with hot methanol. Thesolids were recrystallized from 200 mL of acetone/methanol (1:1 v/v),collected by filtration, washed with methanol, and dried in vacuo togive 8 g of2,4-bis(4-tert-butylphenyl)-6-(2,4-dihydroxyphenyl)-1,3,5-triazine,4-O-benzenesulfonate ester as a pale yellow solid. The structure wasverified by ¹HNMR spectroscopy.

Example A

[0426] Stabilized Polycarbonate Composition

[0427] Polycarbonate plaques are prepared as follows. GE Lexan 105barefoot natural flake polycarbonate resin (melt temperature 310-333°C.) is dry blended with 0.35% stabilizer plus 0.10 wt % Mark® 2112phosphite. The blended compositions are melt-mixed and extruded in aHaake torque rheometer equipped with a a 0.75-inch 25:1 single mixingscrew extruder. The zone temperatures are 246, 265, 295, and 304° C. Theextruded polycarbonate is pulled through a water bath, dried,pelletized, and redried at 120° C. for 4-48 hr in a forced air oven. Thepellets are injection molded at 305-310° C. using an Arburg “Allrounder”hydraulic injection molder to form 2×2.5×0.100-inch plaques. The zonetemperatures are: nozzle—305° C.; nozzle side—310° C.; middle—300° C.;and feed—290° C. The mold temperature is 100° C. Delta E data isobtained using a Macbeth Color Eye Colorimeter with illuminate C, 2°observer, specular component excluded, and UV component included.

[0428] The plaques are exposed in a xenon-arc WeatherOmeter followingASTM G-26 using Test Method B (Miami, Fla. conditions). The conditionsare an irradiance of 0.35 W/m² at 340 nm, alternating cycles of lightand darkness, intermittent water spray, and a black panel temperature of63±3° C. Delta E (total color change) is measured after 400 hr. ofexposure. Polycarbonate compositions containing the para-t-butylCompound have less total color change than the unstabilized controlcomposition.

Example B

[0429] Stabilized Coating Compositions

[0430] Stabilized clear acrylic melamine compositions are prepared andcoated onto steel panels for accelerated weathering testing as follows.The para-tert-butyl compound (2% based on total resin solids) ispre-dissolved in xylenes, alone and in combination with Sanduvor® 3058HALS (0.67% or 1.0% based on total resin solids), and added to the clearacrylic melamine formulation given in Table I. Steel panels pre-coatedwith ED5050A E-coat, 764204 primer, and 542DF716 white base-coat andmeasuring 4″×12″ are obtained from ACT Laboratories, Inc. (Hillsdale,Mich.). The panels are coated with the clear coat formulations using thedraw-down technique (WC-52 Wire-Cators™ obtained from Leneta Co.,Ho-Ho-Kus, N.J.). The clear coats are allowed to flash for 10 min. atambient temperature and cured for 30 min. at 135° C. TABLE I AcrylicMelamine Clear Coat Formulation Material Amount Doresco ® TA 39-14acrylic resin 81.25 g Cymel ® 303 cross-linker 35.0 g Cycat ® 4040catalyst 1.0 g n-Butanol 20.0 g Xylene 16.0 g Product of Example 3^(b)0.364 g^(a)

[0431] Accelerated weathering is carried out with a QTV following ASTMG53 (GM cycle), which is weathering under alternate cycles of (i) UVlight at 70° C. for 8 hours and (ii) condensation with no UV light at50° C. for 4 hr. Specular properties (gloss and distinctness of image,or DOI) are measured as a function of weathering time. Compositionscontaining 2% para-tert-butyl triazine have improved gloss and DOIretention relative to the unstabilized control. Compositions containing1% HALS S-3058 in addition to para-tert-butyl triazine also exhibitimproved gloss and DOI retention.

Example C

[0432] Stabilized Coating Compositions Containing2,4-bis(4-tert-butylphenyl)-6-(2-acetoxy-4-octyloxyphenyl)-1,3,5-triazine

[0433] Canadian patent application 2,162,645 has experimental data whichshows that 2-acetoxy triazine UV absorbers improve the weatherability ofacrylic melamine coating compositions. Weatherability is defined interms of gloss retention. However no data on the yellowing behavior ofthese coating compositions was given. We have found that coatingcompositions containing 2-acetoxy triazines yellow upon exposure to UVlight. We have further discovered that coating compositions containingthe2-(2-acetoxy-4-octyloxyphenyl)-4,6-bis-(4-tert-butylphenyl)-1,3,5-triazineyellow less than those containing2-(2-acetoxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine (Compound A12of the cited patent).

[0434] The coating compositions were weathered using both TVB-313 bulbs(UV light intensity maximum at 313 nm) and UVA-340 bulbs (U lightintensity maximum of 340 nm). The results are summarized in Tables IIand III. Under both weathering conditions, the t-Butyl compoundsurprisingly gave less yellowing. In the UVB-313 example, both equalweight (3.00%) and equimolar amounts (2.31%) of Compound A wereevaluated. Even when compared against the lower, equimolar level ofCompound A, the t-Butyl compound still afforded less yellowing. TABLE IIYELLOWING PERFORMANCE OF STABILIZED COATING COMPOSITIONS UNDER QUV(UVB-313) WEATHERING Hours QUV (UVB-3 13) Exposure Compound F 6 22 131646 1180 1616 2000 3.0% 3.28 5.11 4.67 4.43 4.61 4.33 4.21 t-Butyl^(a)3.0% Compound 4.40 6.66 6.33 6.40 6.36 6.26 5.79 L 2.31% Compound 4.156.45 5.86 6.01 5.84 5.28 4.73 L

[0435] TABLE III YELLOWING PERFORMANCE OF STABILIZED COATINGCOMPOSITIONS UNDER QUV (UVA-340) WEATHERING Hours QUV (UVA-340) ExposureCompound F 6 22 131 500 1158 1704 2334 3.0% t-Buty^(a) 3.01 4.26 4.294.24 3.88 3.51 3.42 3.0% 4.40 5.90 5.52 4.74 4.42 4.80 4.52 Compound L

[0436] Although the present invention is described with reference tocertain preferred embodiments, it is apparent that modifications andvariations thereof may be made by those skilled in the art withoutdeparting from the scope and spirit of this invention as defined by theappended claims.

What is claimed is:
 1. A method of stabilizing a material which issubject to degradation by actinic radiation comprising: incorporatinginto the material an amount of an actinic radiation stabilizercomposition effective to stabilize the material against the effects ofactinic radiation, wherein the actinic radiation stabilizer compositioncomprises a compound of formula (II):

wherein X is hydrogen or a blocking group; each R independently is ahydrocarbyl group of 1 to 21 carbon atoms; R¹ is C₁-C₂₄ alkyl, C₁-C₂₄branched alkyl, C₂-C₂₄ alkenyl, a cycloalkyl from 5-24 carbon atoms, anaraalkyl from 7-24 carbon atoms, —COR⁹, —CO₂R⁹, —CONHR⁹, —SO₂R⁹, C₁-C₁₈alkyl substituted with at least one hydroxy, C₁-C₁₈ alkoxy, C₃-C₁₈alkenoxy, halogen, phenoxy, C₁-C₁₈ alkyl-substituted phenoxy, C₁-C₁₈alkoxy-substituted phenoxy, halogen-substituted phenoxy, —COOH, —COOR⁹,—CONH₂, —CONHR⁹, —CON(R⁹)(R¹⁰), —NH₂, —NHR⁹, —N(R⁹)(R¹⁰), —NHCOR¹¹,—N(R⁹)COR¹¹, —NHCOOR¹¹, —N(⁹)COOR¹¹, —CN, —OCOR¹¹, —OC(O)NHR⁹,—OC(O)N(R⁹)(R¹⁰), glycidyloxy, glycidyl, cyclohexyl optionallysubstituted with hydroxyl or —OCOR¹¹, and C₂-C₅₀ alkyl interrupted by atleast one oxygen atom or carbonyl group and optionally substituted byone or more substituents selected from the group consisting of hydroxyor C₁-C₁₂ alkoxy; wherein R⁹ and R¹⁰ each independently are C₁-C₁₂alkyl, C₃-C₁₂ alkoxyalkyl, C₄-C₁₆ dialkylaminoalkyl, C₅-C₁₂ cycloalkyl,or R⁹ and R¹⁰ taken together are C₃-C₉ alkylene, C₃-C₉ oxoalkylene orC₃-C₉ azaalkylene; and R¹¹ is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, or phenyl;and R³ and R⁴ are each independently hydrogen, hydrocarbyl group of 1 to21 carbon atoms, halogen, hydroxyl, cyano, —O(hydrocarbyl),—O(functional hydrocarbyl), —N(hydrocarbyl)(hydrocarbyl) and mixturesthereof.
 2. The method according to claim 1, wherein at least two of theR groups are methyl and the other R group is methyl, ethyl, butyl,2,2-dimethylpropyl, or phenyl.
 3. The method according to claim 2,wherein each R group is methyl.
 4. The method according to claim 1,wherein R¹ is: an alkyl of 1 to 24 carbon atoms optionally substitutedby at least one hydroxyl, carboxyl, carboalkoxy, amide, epoxy, or aminogroup, and optionally containing at least one carbonyl group, oxygenatom, or nitrogen atom; an alkenyl of 2 to 24 carbon atoms optionallysubstituted by at least one hydroxyl, carboxyl, epoxy, or amino group,and optionally containing at least one carbonyl group, oxygen atom, ornitrogen atom; a cycloalkyl of 5 to 24 carbon atoms optionallysubstituted by at least one hydroxyl, carboxyl, or amino group, andoptionally containing at least one carbonyl group, oxygen atom, ornitrogen atom; an aralkyl of 7 to 24 carbon atoms optionally substitutedby at least one hydroxyl, carboxyl, or amino group, and optionallycontaining at least one carbonyl, oxygen atom, or nitrogen atom; apolyoxyalkylene radical of the formula XII—CH₂—CH(OH)—CH₂—O—(CH2—(CH₂)_(u)—O—)_(mm)—D₁ wherein D₁ is hydrogen,—CH₂—CH(OH)—CH₂—OH,

or R²⁵; a polyoxyalkylene radical of the formula XIII—CO(CH₂)_(u)—O—CH₂—(CH₂)_(u)—O—)_(mm)—D₂ wherein D₂ is —(CH₂)_(u)—CO—R²²or R²⁵; a polyoxyalkylene radical of the formula VIII—YY—O—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₃ wherein D₃ is—(CH₂)_(u)—CO—R²² or R²⁵; a polyoxyalkylene radical of the formula XV—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—B₁—D₄wherein D₄ is hydrogen or R²⁵; a polyoxyalkylene radical of the formulaXVI —CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅ wherein D₅is —NH₂, —NH—(CH₂)₂—COO—R²³ or —O—R²⁵; a polyoxyalkylene radical of theformula XVII—YY—O—CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅ wherein D₅is as defined under formula XVI; a polyoxyalkylene radical of theformula XVIII —(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₆ wherein D₆ is—NH—CO—R²⁴, —OR²⁵, OH or H; a polyoxyalkylene radical of the formula XIX—CH(R²¹)CH₂—(OCH(R¹⁷)—CH₂)_(m)—D₇ wherein D₇ is —OR²⁵, —NHCOR²⁴, or—OCH₂CH₂OR²⁵; R²¹ is hydrogen or C₁-C₁₆ alkyl; R²² is halogen or —O—R²³;R²³ is hydrogen, C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, or aryl-C₁-C₄-alkyl;R²⁴ is hydrogen, C₁-C₁₂ alkyl or aryl; and R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂cycloalkyl, C₃-C₆ alkenyl, C₁-C₁₂ alkylaryl, or aryl-C₁-C₄ alkyl; YY isunsubstituted or substituted C₂-C₂₀ alkylene; B₁ is NH or O; kk is zeroor an integer from 1-16; mm is an integer from 2 to 60; nn is an integerfrom 2 to 6; and u is an integer from 1 to
 4. 5. The method according toclaim 1, wherein R¹ is a hydrocarbyl group having between 4 and 24carbon atoms.
 6. The method according to claim 1, wherein one of R³ andR⁴ is an alkyl group having between 4 and about 24 carbon atoms and theother is hydrogen.
 7. The method according to claim 1, wherein R³ and R⁴are hydrogen.
 8. The method according to claim 1, wherein the compoundof Formula II is present in an amount from about 0.01 to about 20% byweight based on the weight of the material to be stabilized.
 9. Themethod according to claim 1, wherein X is hydrogen.
 10. The methodaccording to claim 1, wherein X is allyl, —COR^(a), —SO₂R^(b),—SiR^(c)R^(d)R^(e), —PR^(f)R^(g), —POR^(f)R^(g), or —CONR^(h), whereinR^(a) is substituted or unsubstituted C₁-C₈ alkyl, halogen, substitutedor unsubstituted C₅-C₁₂ cycloalkyl, substituted or unsubstituted C₂-C,alkenyl, —CH₂—CO—CH₃, substituted or unsubstituted C₁-C₁₂ alkoxy,substituted or unsubstituted phenyl, or substituted or unsubstitutedphenoxy, wherein, if present, the substituent is at least one C₁-C₁₂alkyl, C₁-C₄ alkoxy, halogen, or benzyl; R^(b) is C₁-C₁₂ alkyl, C₆-C₁₀aryl, or C₇-C₁₈ alkylaryl; R^(c), R^(d) or R^(e) each independently isC₁-C₁₈ alkyl, cyclohexyl, phenyl, or C₁-C₁₈ alkoxy; R^(f) or R^(g) eachindependently is substituted or unsubstituted C₁-C₁₂ alkoxy, substitutedor unsubstituted C₁-C₁₂ alkyl, substituted or unsubstituted C₅-C₁₂cycloalkyl, substituted or unsubstituted phenyl, or substituted orunsubstituted phenoxy, wherein, if present, the substituent is at leastone C₁-C₁₂ alkyl, C₁-C₄ alkoxy, halogen or benzyl; and R^(h) issubstituted or unsubstituted C₁-C₈ alkyl, substituted or unsubstitutedC₅-C₁₂ cycloalkyl, substituted or unsubstituted C₂-C₈ alkenyl,—CH₂—CO—CH₃, or substituted or unsubstituted phenyl, wherein, ifpresent, the substituent is at least one C₁-C₁₂ alkyl, C₂-C₈ alkenyl,C₁-C₄ alkoxy, halogen, or benzyl.
 11. The method according to claim 1,wherein the material to be stabilized is an organic polymer.
 12. Themethod according to claim 11, wherein the organic polymer is ahomopolymer, copolymer, or terpolymer.
 13. The method according to claim11, wherein the organic polymer is polycarbonate, polyolefin,polyketone, polyester, acrylic urethane, acrylic melamine, polystyrene,halogen-containing polymer, polymer of α,β-unsaturated acids, polymer ofcyclic ethers, polyacetal, polyphenylene oxide, polyphenylene sulfide,polysulfone, polycarbamate, polyurethane, polyamide, polyamine,polyurea, polyether, polyimide, polyamide-imide, alkyd resin,polyketimines, polysiloxanes, cellulose, rubber, gelatin, oils andwaxes, organic dye, cosmetic products, cellulose-based paperformulations, or combinations thereof.
 14. The method of claim 13,wherein the organic polymer is polyethylene, polyvinyl, polyacrylate,polymethacrylate, polyalkylene, polystyrene, polyacrylamide,polyacrylonitrile, polybutadiene, polychloroprene, epichlorohydrinpolymer, alkylene glycol, alkylene oxide, polyoxymethylene,polyisocyanurate, polycyanate, epoxymelamine resin, polyhydric alcohol,polyamide-imide, polyetherimide, polyesterimide, polyhydantoin,polybenzimidazole, polyester carbonate, polyehter sulfone, polyetherketone, drying and non-drying alkyd resins, unsaturated polyester resin,epoxymelamine resins, photographic film paper, ink, or combinationsthereof.
 15. The method of claim 11, wherein the organic polymer ispolyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinylstearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral,polyallyl alcohol, polyallyl amine, polyallyl glycidyl ether, polyallylphthalate, polyallyl melamine, polyethylene terephthalate, ABS(acrylonitrile-butadiene-styrene), SAN (styrene-acrylonitrile), or acombination thereof.
 16. The method according to claim 1, wherein thecompound of Formula II is incorporated into the material by chemicalbonding during and/or subsequent to the preparation of the material. 17.The method according to claim 1 further comprising incorporating intothe material at least one additional additive, wherein the additionaladditive is antioxidant, ultraviolet light absorber, ultraviolet lightstabilizer, metal deactivator, phosphite, phosphonite, hydroxylamine,nitrone, thiosynergist, peroxide scavenger, polyamide stabilizer,nucleating agent, filler, reinforcing agent, plasticizer, lubricant,emulsifier, pigment, rheological additive, flameproofing agent,antistatic agent, blowing agent, benzofuranone, or indolinone.
 18. Themethod according to claim 17, wherein the additional additive ishindered amine light stabilizer.
 19. The method of claim 18, wherein thehindered amine is at least onebis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate;bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;bis(1,2,2,6,6-pentamethylpiperidin-4-yl)n-butyl3,5-di-tert-butyl-4-hydroxybenzylmalonate; a condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid; a condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine;tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate;1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);4-benzoyl-2,2,6,6-tetramethylpiperidine;4-stearyloxy-2,2,6,6-tetramethylpiperidine;bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; a condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine; a condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane; a condensate of2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3- aminopropylamino)ethane;8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione;3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;a mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine; a condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; a condensate of1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and4-butylamino-2,2,6,6-tetramethylpiperidine;2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;oxo-piperanzinyl-triazines; or a condensate of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decaneand epichlorohydrin.
 20. The method according to claim 17, wherein theUV light absorber is benzotriazole, triazine, benzophenone, ester ofbenzoic acids, acrylate, sterically hindered amine, or oxamide.
 21. Themethod according to claim 20, wherein said additional additive is abenzotriazole.
 22. The method according to claim 21, wherein thebenzotriazole comprises at least one2-(2′-hydroxy-5′-methylphenyl)-benzotriazole;2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole;2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole;2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole;2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole;2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)-benzotriazole;2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole;2-(3′,5′-di-tert-amyl-2′-hydroxphenyl)benzotriazole;2-(3′,5′-bis(ana-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole; amixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3 ′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole;2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];and a transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]benzotriazolewith polyethylene glycol.
 23. A method of protecting a substrate againstdegradation by actinic radiation comprising applying to the substrate acoating containing an actinic radiation stabilizer composition in anamount effective to reduce the amount of actinic radiation impinging onthe substrate, wherein the actinic radiation stabilizer compositioncomprises a compound of formula (II):

wherein X is hydrogen or a blocking group; each R independently is ahydrocarbyl group of 1 to 21 carbon atoms; R¹ is C₁-C₂₄ alkyl, C₁-C₂₄branched alkyl, C₂-C₂₄ alkenyl, a cycloalkyl from 5-24 carbon atoms, anaraalkyl from 7-24 carbon atoms, —COR⁹, —CO₂R⁹, —CONHR⁹, —SO₂R⁹, C₁-C₁₈alkyl substituted with at least one hydroxy, C₁-C₁₈ alkoxy, C₃-C₁₈alkenoxy, halogen, phenoxy, C₁-C₁₈ alkyl-substituted phenoxy, C₁-C₁₈alkoxy-substituted phenoxy, halogen-substituted phenoxy, —COOH, —COOR⁹,—CONH₂, —CONHR⁹, —CON(R⁹)(R¹⁰), —NH₂, —NHR⁹, —N(R⁹)(R¹⁰), —NHCOR¹¹,—N(R⁹)COR¹¹, —NHCOOR¹¹, —N(⁹)COOR¹¹, —CN, —OCOR¹¹, —OC(O)NHR⁹,—OC(O)N(R⁹)(R¹⁰), glycidyloxy, glycidyl, cyclohexyl optionallysubstituted with hydroxyl or —OCOR¹¹, and C₂-C₅₀ alkyl interrupted by atleast one oxygen atom or carbonyl group and optionally substituted byone or more substituents selected from the group consisting of hydroxyor C₁-C₁₂ alkoxy; wherein R⁹ and R¹⁰ each independently are C₁-C₁₂alkyl, C₃-C₁₂ alkoxyalkyl, C₄-C₁₆ dialkylaminoalkyl, C₅-C₁₂ cycloalkyl,or R⁹ and R¹⁰ taken together are C₃-C₉ alkylene, C₃-C₉ oxoalkylene orC₃-C₉ azaalkylene; and R¹¹ is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, or phenyl;and R³ and R⁴ are each independently hydrogen, hydrocarbyl group of 1 to21 carbon atoms, halogen, hydroxyl, cyano, —O(hydrocarbyl),—O(functional hydrocarbyl), —N(hydrocarbyl)(hydrocarbyl) and mixturesthereof.
 24. The method according to claim 23, wherein the coating is inthe form of a film.
 25. A method of stabilizing a material which issubject to degradation by actinic radiation comprising: incorporatinginto the material an amount of an actinic radiation stabilizercomposition effective to stabilize the material against the effects ofactinic radiation, wherein the actinic radiation stabilizer compositioncomprises a compound of formula (III):

wherein X is hydrogen or a blocking group; each R independently is ahydrocarbyl group of 1 to 21 carbon atoms; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl group of 1 to 21 carbon atoms,halogen, hydroxyl, cyano, —O(hydrocarbyl), —O(functional hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl) and mixtures thereof; r is an integerbetween 2 and 4; and D, when r is 2, is selected from the groupconsisting of C₂-C₁₆ alkylene, C₄-C₁₂ alkenylene, xylylene, C₄-C₂₀alkylene which is interrupted by one or more oxygen atoms,hydroxy-substituted C₃-C₂₀ alkyl which is interrupted by one or moreoxygen atoms, —CH₂CH(OH)CH₂O—R¹⁵—OCH₂CH(OH)CH₂—, —CO—R₁₆—CO—,—CO—NH—R¹⁷—NH—CO—, —(CH₂)_(s)—COO—R¹⁸—OCO—(CH₂)_(s)— a polyoxyalkylenebridge member of the formula XX—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—CH₂—CH(OH)—CH₂—  (XX), apolyoxyalkylene bridge member of the formula XXI—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—  (XXI), apolyoxyalkylene bridge member of the formula XXII—YY—O—CO(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—COO—YY—  (XXII), apolyoxyalkylene bridge member of the formula XXIII—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)C_(nn)H_(2nn)—B₁—CO—CH(R²¹)—(CH₂)_(kk)—  (XXIII),a polyoxyalkylene bridge member of the formula XXIV—COCH(R²¹)CH₂NH(C_(nn)H_(2nn)O)_(mm)C_(nn)H_(2nn)—NHCH₂—CH(R²¹)CO—  (XXIV)a polyoxyalkylene bridge member of the formula XXV—YY—O—CO—(CH₂)₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—NH—(CH₂)₂COO—YY—  (XXV),a polyoxyalkylene bridge member of the formula XXVI—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—  (XXVI), and a polyoxyalkylenebridge member of the formula XXVII—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(a)—(O—CH₂—CH₂)_(b)—(O—CH₂—CH(CH₃)_(c)—  (XXVII),wherein a+c=2.5 and b=8.5 to 40.5 or a+c=2 to 33 and b=0, R²¹ ishydrogen or C₁-C₁₆ alkyl, R²² is halogen or —O—R²³, R²³ is hydrogen,C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, or aryl-C₁-C₄-alkyl, R²⁴ is hydrogen,C₁-C₁₂ alkyl or aryl; R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆alkenyl, C₁-C₁₂ alkylaryl or aryl-C₁-C₄ alkyl; R²⁶ is hydrogen or C₁-C₄alkyl; R²⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy,halogen or aryl-C₁-C₄ alkyl; R²⁸ and R²⁹ independently of one anotherare hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, or C₁-C₁₈ alkoxy, or halogen;R³⁰ is hydrogen, C₁-C₄ alkyl or CN; YY is unsubstituted or substitutedC₂-C₂₀ alkyl; B₁ is HN or O; kk is zero or an integer from 1-16; mm isan integer from 2 to 60; nn is an integer from 2 to 6; u is an integerfrom 1 to 4; when r is 3, D is

and when r is 4, D is

wherein R¹⁹ is C₃-C₁₀ alkanetriyl and R²⁰ is C₄-C₁₀ alkanetetryl; and sis 1-6; R¹⁵ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀dithiaalkylene, phenylene, naphthylene, diphenylene, or C₂-C₆alkenylene, or phenylene-XX-phenylene wherein XX is —O—, —S—, —SO₂—,—CH₂—, or (CH₃)₂—; R¹⁶ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀dithiaalkylene, phenylene, naphthylene, diphenylene, or C₂-C₆ alkenyleneprovided that when r is 3 the alkenylene has at least 3 carbons; R¹⁷ isC₂-C₁₀ alkylene, phenylene, naphthylene, diphenylene, or C₂-C₆alkenylene, methylenediphenylene, or C₄-C₁₅ alkylphenylene; and R¹⁸ isC₂-C₁₀ alkylene, or C₄-C₂₀ alkylene interrupted by one or more oxygenatoms.
 26. A method of protecting a substrate against degradation byactinic radiation comprising applying to the substrate a coatingcontaining an actinic radiation stabilizer composition in an amounteffective to reduce the amount of actinic radiation impinging on thesubstrate, wherein the actinic radiation stabilizer compositioncomprises a compound a compound of formula (III):

wherein X is hydrogen or a blocking group; each R independently is ahydrocarbyl group of 1 to 21 carbon atoms; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl group of 1 to 21 carbon atoms,halogen, hydroxyl, cyano, —O(hydrocarbyl), —O(functional hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl) and mixtures thereof; r is an integerbetween 2 and 4; and D, when r is 2, is selected from the groupconsisting of C₂-C₁₆ alkylene, C₄-C₁₂ alkenylene, xylylene, C₄-C₂₀alkylene which is interrupted by one or more oxygen atoms,hydroxy-substituted C₃-C₂₀ alkyl which is interrupted by one or moreoxygen atoms, —CH₂CH(OH)CH₂O—R¹⁵—OCH₂CH(OH)CH₂—, —CO—R₁₆—CO—,—CO—NH—R¹⁷—NH—CO—, —(CH₂)_(s)—COO—R¹⁸—OCO—(CH₂)_(s)— a polyoxyalkylenebridge member of the formula XX—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—CH₂—CH(OH)—CH₂—  (XX), apolyoxyalkylene bridge member of the formula XXI—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—  (XXI), apolyoxyalkylene bridge member of the formula XXII—YY—O—CO(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—COO—YY—  (XXII), apolyoxyalkylene bridge member of the formula XXIII—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)C_(nn)H_(2nn)—B₁—CO—CH(R²¹)—(CH₂)_(kk)—  (XXIII),a polyoxyalkylene bridge member of the formula XXIV—COCH(R²¹)CH₂NH(C_(nn)H_(2nn)O)_(mm)C_(nn)H_(2nn)—NHCH₂—CH(R²¹)CO—  (XXIV)a polyoxyalkylene bridge member of the formula XXV—YY—O—CO—(CH₂)₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—NH—(CH₂)₂COO—YY—  (XXV),a polyoxyalkylene bridge member of the formula XXVI—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—  (XXVI), and a polyoxyalkylenebridge member of the formula XXVII—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(a)—(O—CH₂—CH₂)_(b)—(O—CH₂—CH(CH₃)_(c)—  (XXVII),wherein a+c=2.5 and b=8.5 to 40.5 or a+c=2 to 33 and b=0, R²¹ ishydrogen or C₁-C₁₆ alkyl, R²² is halogen or —O—R²³, R²³ is hydrogen,C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, or aryl-C₁-C₄-alkyl, R²⁴ is hydrogen,C₁-C₁₂ alkyl or aryl; R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆alkenyl, C₁-C₁₂ alkylaryl or aryl-C₁-C₄ alkyl; R²⁶ is hydrogen or C₁-C₄alkyl; R²⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy,halogen or aryl-C₁-C₄ alkyl; R²⁸ and R²⁹ independently of one anotherare hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, or C₁-C₁₈ alkoxy, or halogen;R³⁰ is hydrogen, C₁-C₄ alkyl or CN; YY is unsubstituted or substitutedC₂-C₂₀ alkyl; B₁ is HN or O; kk is zero or an integer from 1-16; mm isan integer from 2 to 60; nn is an integer from 2 to 6; u is an integerfrom 1 to 4; when r is 3, D is

and when r is 4, D is

wherein R¹⁹ is C₃-C₁₀ alkanetriyl and R²⁰ is C₄-C₁₀ alkanetetryl; and sis 1-6; R¹⁵ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀dithiaalkylene, phenylene, naphthylene, diphenylene, or C₂-C₆alkenylene, or phenylene-XX-phenylene wherein XX is —O—, —S—, —SO₂—,—CH₂—, or (CH₃)₂—; R¹⁶ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀dithiaalkylene, phenylene, naphthylene, diphenylene, or C₂-C₆ alkenyleneprovided that when r is 3 the alkenylene has at least 3 carbons; R¹⁷ isC₂-C₁₀ alkylene, phenylene, naphthylene, diphenylene, or C₂-C₆alkenylene, methylenediphenylene, or C₄-C₁₅ alkylphenylene; and R¹⁸ isC₂-C₁₀ alkylene, or C₄-C₂₀ alkylene interrupted by one or more oxygenatoms.
 27. A method of stabilizing a material which is subject todegradation by actinic radiation comprising: incorporating into thematerial an amount of an actinic radiation stabilizer compositioneffective to stabilize the material against the effects of actinicradiation, wherein the actinic radiation stabilizer compositioncomprises a compound of formula (IV):

wherein each R independently is a hydrocarbyl group of 1 to 21 carbonatoms; R³ and R⁴ are each independently hydrogen, hydrocarbyl group of 1to 21 carbon atoms, halogen, hydroxyl, cyano, —O(hydrocarbyl),—O(functional hydrocarbyl), —N(hydrocarbyl)(hydrocarbyl) and mixturesthereof; L is hydrogen, C₁-C₂₄ alkyl, C₁-C₂₄ branched alkyl, C₃-C₆alkenyl, —COR¹², —COOR¹², —CONHR¹², —SO₂R¹³, C₁-C₁₈ alkyl which issubstituted with at least one hydroxy, C₁-C₁₈ alkoxy, C₃-C₁₈ alkenoxy,halogen, phenoxy, C₁-C₁₈ alkyl-substituted phenoxy, C₁-C₁₈alkoxy-substituted phenoxy, halogen-substituted phenoxy, —COOH, —COOR⁹,—CONH₂, —CONHR⁹, —CON(R⁹)(R¹⁰), —NH₂, —NHR⁹, —N(R⁹)(R¹⁰), —NHCOR¹¹,—N(R⁹)COR¹¹, —NHCOOR¹¹, —N(R⁹)COOR¹¹, —CN, —OCOR¹¹, —OC(O)NHR⁹,—OC(O)N(R⁹)(R¹⁰), glycidyloxy, glycidyl, cyclohexyl optionallysubstituted with hydroxyl or —OCOR¹¹ or C₂-C₅₀ alkyl optionallyinterrupted by at least one oxygen atom or carbonyl group and optionallysubstituted by at least one substituents selected from the groupconsisting of hydroxy and C₁-C₁₂ alkoxy, wherein R⁹ and R¹⁰independently of one another are C₁-C₁₂ alkyl, C₃-C₁₂ alkoxyalkyl,C₄-C₁₆ dialkylaminoalkyl, C₅-C₁₂ cycloalkyl, or R⁹ and R¹⁰ takentogether are C₃-C₉ alkylene, C₃-C₉ oxoalkylene, C₃-C₉ azaalkylene; R¹¹is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl; R¹² is C₁-C₁₈ alkyl, C₂-C₁₈alkenyl, phenyl, C₁-C₁₂ alkoxy, phenoxy, C₁-C₁₂ alkylamino, phenylamino,tolylamino or naphthylamino; and R¹³ is C₁-C₁₂ alkyl, phenyl, naphthylor C₇-C₁₄ alkylphenyl; r is an integer between 2 and 4; and X′, when ris 2, is selected from the group consisting of C₂-C₁₆ alkylene, C₄-C₁₂alkenylene, xylylene, C₄-C₂₀ alkylene which is interrupted by one ormore oxygen atoms, hydroxy-substituted C₃-C₂₀ alkyl which is interruptedby one or more oxygen atoms, —CH₂CH(OH)CH₂OR¹⁵—OCH₂CH(OH)CH₂—,—(CH₂)_(s)—COO—R¹⁸—OCO—(CH₂)_(s)— a polyoxyalkylene bridge member of theformula XX—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—CH₂—CH(OH)—CH₂—  (XX), apolyoxyalkylene bridge member of the formula XXI—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—  (XXI), apolyoxyalkylene bridge member of the formula XXII—YY—O—CO(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—COO—YY—  (XXII), apolyoxyalkylene bridge member of the formula XXIII—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)C_(nn)H_(2nn)—B₁—CO—CH(R²¹)—(CH₂)_(kk)—  (XXIII),a polyoxyalkylene bridge member of the formula XXIV—COCH(R²¹)CH₂NH(C_(nn)H_(2nn)O)_(mm)C_(nn)H_(2nn)—NHCH₂—CH(R²¹)CO—  (XXIV)a polyoxyalkylene bridge member of the formula XXV—YY—O—CO—(CH₂)₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—NH—(CH₂)₂COO—YY—  (XXV),a polyoxyalkylene bridge member of the formula XXVI—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—  (XXVI), and a polyoxyalkylenebridge member of the formula XXVII—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(a)—(O—CH₂—CH₂)_(b)—(O—CH₂—CH(CH₃)_(c)—  (XXVII),wherein a+c=2.5 and b=8.5 to 40.5 or a+c=2 to 33 and b=0, R²¹ ishydrogen or C₁-C₁₆ alkyl, R²² is halogen or —O—R²³, R²³ is hydrogen,C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, or aryl-C₁-C₄-alkyl, R²⁴ is hydrogen,C₁-C₁₂ alkyl or aryl; R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆alkenyl, C₁-C₁₂ alkylaryl or aryl-C₁-C₄ alkyl; R²⁶ is hydrogen or C₁-C₄alkyl; R²⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy,halogen or aryl-C₁-C₄ alkyl; R²⁸ and R²⁹ independently of one anotherare hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, or C₁-C₁₈ alkoxy, or halogen;R³⁰ is hydrogen, C₁-C₄ alkyl or CN; YY is unsubstituted or substitutedC₂-C₂₀ alkyl; B₁ is HN or O; kk is zero or an integer from 1-16; mm isan integer from 2 to 60; nn is an integer from 2 to 6; u is an integerfrom 1 to 4; when r is 3, D is

and when r is 4, D is

wherein R¹⁹ is C₃-C₁₀ alkanetriyl and R²⁰ is C₄-C₁₀ alkanetetryl; and sis 1-6; R¹⁵ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀dithiaalkylene, phenylene, naphthylene, diphenylene, or C₂-C₆alkenylene, or phenylene-XX-phenylene wherein XX is —O—, —S—, —SO₂—,—CH₂—, or (CH₃)₂—; R¹⁶ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀dithiaalkylene, phenylene, naphthylene, diphenylene, or C₂-C₆ alkenyleneprovided that when r is 3 the alkenylene has at least 3 carbons; R¹⁷ isC₂-C₁₀ alkylene, phenylene, naphthylene, diphenylene, or C₂-C₆alkenylene, methylenediphenylene, or C₄-C₁₅ alkylphenylene; and R¹⁸ isC₂-C₁₀ alkylene, or C₄-C₂₀ alkylene interrupted by one or more oxygenatoms.
 28. A method of protecting a substrate against degradation byactinic radiation comprising applying to the substrate a coatingcontaining an actinic radiation stabilizer composition in an amounteffective to reduce the amount of actinic radiation impinging on thesubstrate, wherein the actinic radiation stabilizer compositioncomprises a compound a compound of formula (IV):

wherein each R independently is a hydrocarbyl group of 1 to 21 carbonatoms; R³ and R⁴ are each independently hydrogen, hydrocarbyl group of 1to 21 carbon atoms, halogen, hydroxyl, cyano, —O(hydrocarbyl),—O(functional hydrocarbyl), —N(hydrocarbyl)(hydrocarbyl) and mixturesthereof; L is hydrogen, C₁-C₂₄ alkyl, C₁-C₂₄ branched alkyl, C₃-C₆alkenyl, —COR¹², —COOR¹², —CONHR¹², —SO₂R¹³, C₁-C₁₈ alkyl which issubstituted with at least one hydroxy, C₁-C₁₈ alkoxy, C₃-C₁₈ alkenoxy,halogen, phenoxy, C₁-C₁₈ alkyl-substituted phenoxy, C₁-C₁₈alkoxy-substituted phenoxy, halogen-substituted phenoxy, —COOH, —COOR⁹,—CONH₂, —CONHR⁹, —CON(R⁹)(R¹⁰), —NH₂, —NHR⁹, —N(R⁹)(R¹⁰), —NHCOR¹¹,—N(R⁹)COR¹¹, —NHCOOR¹¹, —N(R⁹)COOR¹¹, —CN, —OCOR¹¹, —OC(O)NHR⁹,—OC(O)N(R⁹)(R¹⁰), glycidyloxy, glycidyl, cyclohexyl optionallysubstituted with hydroxyl or —OCOR¹¹ or C₂-C₅₀ alkyl optionallyinterrupted by at least one oxygen atom or carbonyl group and optionallysubstituted by at least one substituents selected from the groupconsisting of hydroxy and C₁-C₁₂ alkoxy, wherein R⁹ and R¹⁰independently of one another are C₁-C₁₂ alkyl, C₃-C₁₂ alkoxyalkyl,C₄-C₁₆ dialkylaminoalkyl, C₅-C₁₂ cycloalkyl, or R⁹ and R¹⁰ takentogether are C₃-C₉ alkylene, C₃-C₉ oxoalkylene, C₃-C₉ azaalkylene; R¹¹is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl; R¹² is C₁-C₁₈ alkyl, C₂-C₁₈alkenyl, phenyl, C₁-C₁₂ alkoxy, phenoxy, C₁-C₁₂ alkylamino, phenylamino,tolylamino or naphthylamino; and R¹³ is C₁-C₁₂ alkyl, phenyl, naphthylor C₇-C₁₄ alkylphenyl; r is an integer between 2 and 4; and X′, when ris 2, is selected from the group consisting of C₂-C₁₆ alkylene, C₄-C₁₂alkenylene, xylylene, C₄-C₂₀ alkylene which is interrupted by one ormore oxygen atoms, hydroxy-substituted C₃-C₂₀ alkyl which is interruptedby one or more oxygen atoms, —CH₂CH(OH)CH₂OR¹⁵—OCH₂CH(OH)CH₂—,—(CH₂)_(s)—COO—R¹⁸—OCO—(CH₂)_(s)— a polyoxyalkylene bridge member of theformula XX—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—CH₂—CH(OH)—CH₂—  (XX), apolyoxyalkylene bridge member of the formula XXI—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—  (XXI), apolyoxyalkylene bridge member of the formula XXII—YY—O—CO(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—COO—YY—  (XXII), apolyoxyalkylene bridge member of the formula XXIII—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)C_(nn)H_(2nn)—B₁—CO—CH(R²¹)—(CH₂)_(kk)—  (XXIII),a polyoxyalkylene bridge member of the formula XXIV—COCH(R²¹)CH₂NH(C_(nn)H_(2nn)O)_(mm)C_(nn)H_(2nn)—NHCH₂—CH(R²¹)CO—  (XXIV)a polyoxyalkylene bridge member of the formula XXV—YY—O—CO—(CH₂)₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—NH—(CH₂)₂COO—YY—  (XXV),a polyoxyalkylene bridge member of the formula XXVI—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—  (XXVI), and a polyoxyalkylenebridge member of the formula XXVII—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(a)—(O—CH₂—CH₂)_(b)—(O—CH₂—CH(CH₃)_(c)—  (XXVII),wherein a+c=2.5 and b=8.5 to 40.5 or a+c=2 to 33 and b=0, R²¹ ishydrogen or C₁-C₁₆ alkyl, R²² is halogen or —O—R²³, R²³ is hydrogen,C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, or aryl-C₁-C₄-alkyl, R²⁴ is hydrogen,C₁-C₁₂ alkyl or aryl; R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆alkenyl, C₁-C₁₂ alkylaryl or aryl-C₁-C₄ alkyl; R²⁶ is hydrogen or C₁-C₄alkyl; R²⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy,halogen or aryl-C₁-C₄ alkyl; R²⁸ and R²⁹ independently of one anotherare hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, or C₁-C₁₈ alkoxy, or halogen;R³⁰ is hydrogen, C₁-C₄ alkyl or CN; YY is unsubstituted or substitutedC₂-C₂₀ alkyl; B₁ is HN or O; kk is zero or an integer from 1-16; mm isan integer from 2 to 60; nn is an integer from 2 to 6; u is an integerfrom 1 to 4; when r is 3, D is

and when r is 4, D is

wherein R¹⁹ is C₃-C₁₀ alkanetriyl and R²⁰ is C₄-C₁₀ alkanetetryl; and sis 1-6; R¹⁵ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀dithiaalkylene, phenylene, naphthylene, diphenylene, or C₂-C₆alkenylene, or phenylene-XX-phenylene wherein XX is —O—, —S—, —SO₂—,—CH₂—, or (CH₃)₂—; R¹⁶ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀dithiaalkylene, phenylene, naphthylene, diphenylene, or C₂-C₆ alkenyleneprovided that when r is 3 the alkenylene has at least 3 carbons; R¹⁷ isC₂-C₁₀ alkylene, phenylene, naphthylene, diphenylene, or C₂-C₆alkenylene, methylenediphenylene, or C₄-C₁₅ alkylphenylene; and R¹⁸ isC₂-C₁₀ alkylene, or C₄-C₂₀ alkylene interrupted by one or more oxygenatoms.
 29. A method of stabilizing a material which is subject todegradation by actinic radiation comprising: incorporating into thematerial an amount of an actinic radiation stabilizer compositioneffective to stabilize the material against the effects of actinicradiation, wherein the actinic radiation stabilizer compositioncomprises a compound of formula (V):

wherein X is hydrogen or a blocking group; each R independently is ahydrocarbyl group of 1 to 21 carbon atoms; R³ is hydrogen, hydrocarbylgroup of 1 to 21 carbon atoms, halogen, hydroxyl, cyano,—O(hydrocarbyl), —O(functional hydrocarbyl), or —N(hydrocarbyl)₂; R⁴ isa straight chain alkyl of 1 to 12 carbon atoms, branched chain alkyl of1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkylsubstituted by cyclohexyl, alkyl interrupted by cyclohexyl, alkylsubstituted by phenylene, alkyl interrupted by phenylene, benzylidene,—S—, —S—S—, —S—E—S—,—SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO₂—,—CH₂—NH—E—NH—CH₂—, and

wherein E is selected from the group consisting of alkyl of 2 to 12carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted bycyclohexyl of 8 to 12 carbon atoms, alkyl terminated by cyclohexyl of 8to 12 carbon atoms; r is an integer between 2 and 4; and L is selectedfrom a hydrogen, hydrocarbyl, further substituted by halogen, hydroxyl,cyano, —O(hydrocarbyl), —O(functional hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl), —N(functional hydrocarbyl)(functionalhydrocarbyl), —S(hydrocarbyl), —S(functional hydrocarbyl),—SO₂(hydrocarbyl), —SO₃(hydrocarbyl), —SO₂(functional hydrocarbyl),—SO₃(functional hydrocarbyl), —COO(hydrocarbyl), —COO(functionalhydrocarbyl), —CO(hydrocarbyl), —CO(functional hydrocarbyl),—OCO(hydrocarbyl), —OCO(functional hydrocarbyl), —CONH₂,—CONH(hydrocarbyl), —CONH(functional hydrocarbyl), —CON(hydrocarbyl)(hydrocarbyl), —CON(functional hydrocarbyl)(hydrocarbyl),—CON(functional hydrocarbyl)(functional hydrocarbyl), or a hydrocarbylgroup substituted by any of the above groups.
 30. A method of protectinga substrate against degradation by actinic radiation comprising applyingto the substrate a coating containing an actinic radiation stabilizercomposition in an amount effective to reduce the amount of actinicradiation impinging on the substrate, wherein the actinic radiationstabilizer composition comprises a compound a compound of formula (V):

wherein X is hydrogen or a blocking group; each R independently is ahydrocarbyl group of 1 to 21 carbon atoms; R³ is hydrogen, hydrocarbylgroup of 1 to 21 carbon atoms, halogen, hydroxyl, cyano,—O(hydrocarbyl), —O(functional hydrocarbyl), or —N(hydrocarbyl)₂; R⁴ isa straight chain alkyl of 1 to 12 carbon atoms, branched chain alkyl of1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkylsubstituted by cyclohexyl, alkyl interrupted by cyclohexyl, alkylsubstituted by phenylene, alkyl interrupted by phenylene, benzylidene,—S—, —S—S—, —S—E—S—,—SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO₂—,—CH₂—NH—E—NH—CH₂—, and

wherein E is selected from the group consisting of alkyl of 2 to 12carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted bycyclohexyl of 8 to 12 carbon atoms, alkyl terminated by cyclohexyl of 8to 12 carbon atoms; r is an integer between 2 and 4; and L is selectedfrom a hydrogen, hydrocarbyl, further substituted by halogen, hydroxyl,cyano, —O(hydrocarbyl), —O(functional hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl), —N(functional hydrocarbyl)(functionalhydrocarbyl), —S(hydrocarbyl), —S(functional hydrocarbyl),—SO₂(hydrocarbyl), —SO₃(hydrocarbyl), —SO₂(functional hydrocarbyl),—SO₃(functional hydrocarbyl), —COO(hydrocarbyl), —COO(functionalhydrocarbyl), —CO(hydrocarbyl), —CO(functional hydrocarbyl),—OCO(hydrocarbyl), —OCO(functional hydrocarbyl), —CONH₂,—CONH(hydrocarbyl), —CONH(functional hydrocarbyl), —CON(hydrocarbyl)(hydrocarbyl), —CON(functional hydrocarbyl)(hydrocarbyl),—CON(functional hydrocarbyl)(functional hydrocarbyl), or a hydrocarbylgroup substituted by any of the above groups.